Thermosetting powder coating compositions comprising peroxydicarbonates

ABSTRACT

The invention relates to thermosetting powder coating compositions as disclosed herein, said compositions comprising one or more unsaturated resins comprising ethylenic unsaturations, one or more curing agents, and one or more thermal radical initiators, wherein at least one of the initiators is a peroxydicarbonate-X. The invention further relates to a process for making said thermosetting powder coating compositions and processes for coating an article with said thermosetting powder coating compositions. The invention further relates to cured thermosetting powder coating compositions obtained by curing of the thermosetting powder coating compositions of the invention. The invention further relates to an article having coated thereon said thermosetting powder coating composition as well as to an article having coated and cured thereon said thermosetting powder coating composition. The invention further relates to the use of said thermosetting powder coating compositions, to the use of an article having coated thereon said thermosetting powder coating compositions and to the use of an article having coated and cured thereon said thermosetting powder coating compositions. The invention further relates to various uses of either the thermosetting powder coating compositions of the invention, or the cured thermosetting powder coating compositions of the invention or of articles having coated thereon the thermosetting powder coating composition of the invention, or of articles having coated and cured thereon the thermosetting powder coating composition of the invention. The invention further relates to a method for enabling the fast heat-curing of a thermosetting powder coating composition at low temperature. The invention further relates to a method for enhancing the chemical resistance of a powder coating obtained by heat curing of the thermosetting powder coating composition of the invention at low temperature.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. national phase of International ApplicationNo. PCT/EP2017/074534 filed 27 Sep. 2017, which designated the U.S. andclaims priority to EP Patent Application No. 16191173.0 filed 28 Sep.2016, EP Patent Application No. 16191174.8 filed 28 Sep. 2016, and EPPatent Application No. 16191175.5 filed 28 Sep. 2016, the entirecontents of each of which are hereby incorporated by reference.

BACKGROUND AND SUMMARY

The invention relates to thermosetting powder coating compositions asthese are disclosed herein. The invention further relates to a processfor making said thermosetting powder coating compositions and processesfor coating an article with said thermosetting powder coatingcompositions. The invention further relates to cured thermosettingpowder coating compositions obtained by curing of the thermosettingpowder coating compositions of the invention. The invention furtherrelates to an article having coated thereon said thermosetting powdercoating composition as well as to an article having coated and curedthereon said thermosetting powder coating composition. The inventionfurther relates to the use of said thermosetting powder coatingcompositions, to the use of an article having coated thereon saidthermosetting powder coating compositions and to the use of an articlehaving coated and cured thereon said thermosetting powder coatingcompositions. The invention further relates to various uses of eitherthe thermosetting powder coating compositions of the invention, or thecured thermosetting powder coating compositions of the invention or ofarticles having coated thereon the thermosetting powder coatingcomposition of the invention, or of articles having coated and curedthereon the thermosetting powder coating composition of the invention.The invention further relates to a method for enabling the fastheat-curing of a thermosetting powder coating composition at lowtemperature. The invention further relates to a method for enhancing thechemical resistance of a powder coating obtained by heat curing of thethermosetting powder coating composition of the invention at lowtemperature.

Powder coating compositions (commonly referred to as powders) which aredry, finely divided, free flowing, solid materials at room temperatureand at atmospheric pressure, have gained considerable popularity inrecent years over liquid coating compositions for a number of reasons.For one powder coatings are user and environmentally friendly materialssince they are virtually free of harmful volatile organic solventscarriers that are normally present in liquid coating compositions.Therefore, powder coatings give off little, if any, volatile materialsto the environment when cured. This eliminates the solvent emissionproblems associated with liquid coating compositions such as airpollution and dangers to the health of workers employed in coatingoperations. Powder coating compositions are also clean and convenient touse since they are applied in a clean manner over the substrate becausethey are in dry solid form. The powders are easily swept up in the eventof a spill and do not require special cleaning and spill containmentsupplies, as do liquid coating compositions. Working hygiene is thusimproved. Moreover, powder coating compositions are essentially 100%recyclable since the sprayed powders can be fully reclaimed andrecombined with fresh powder feed. Recycling of liquid coatings duringapplication is often not done, which leads to increased waste andhazardous waste disposal costs. In addition, powder coating compositionsare ready to use, i.e., no thinning or dilution is required.

Powder coating compositions are typically applied on a substrate via anelectrostatic spray process; the powder coating composition is dispersedin an air stream and passed through a corona discharge field where theparticles acquire an electrostatic charge. The charged particles areattracted to and deposited on the grounded article to be coated. Thearticle, usually at room temperature, is then placed in an oven wherethe powder melts and forms a powder coating. A hybrid process based on acombination of high voltage electrostatic charging and fluidized-bedapplication techniques (electrostatic fluidized bed) has evolved, aswell as triboelectric spray application methods. Powder coatingcompositions and their process of application are the preferred coatingcompositions and process for coating many familiar items such as lawnand garden equipment, patio and other metal furniture, electricalcabinets, lighting, shelving and store fixtures, and many automotivecomponents. Today, powder coating compositions are widely accepted, withthousands of installations in the factories of original equipmentmanufacturers (OEMS) and custom coating job shops.

Powder coating compositions can be thermosetting or thermoplastic.

The invention relates to the field of thermosetting powder coatingcompositions. The preparation of thermosetting powder coatingcompositions is described by Misev in ‘Powder Coatings, Chemistry andTechnology’ (pp. 224-300; 1991, John Wiley& Sons Ltd.).

Despite their many advantages, powder coatings are generally notemployed in coating heat sensitive substrates, such as wood andplastics. Heat sensitive substrates demand curing at low temperaturesfor example heat curing at temperatures as high as 130° C., to avoidsignificant substrate degradation and/or deformation. For instance whenwood composites, e.g. particle board, fiber board and other substratesthat comprise a significant amount of wood are heated to the high curingtemperatures required for traditional powders (typically temperatureshigher than 140° C.), the residual moisture and resinous binders presentin the wood composites for substrate integrity caused to invariablyevolve from the substrate. Outgassing of the volatiles during curing,results in severe blisters, craters, pinholes and other surface defectsin the hardened film finish. Furthermore, overheating causes the woodcomposites to become brittle, friable, charred and otherwise worsened inphysical and chemical properties. This is not acceptable from both afilm quality and product viewpoint.

Low temperature UV curable thermosetting powder coating compositionswere proposed for coating heat sensitive substrates. UV powders stillrequire exposure to heat, which is above either the glass transitiontemperature (T_(g)) or melting temperature (T_(m)) to sufficiently meltand flow out the powders into a continuous molten film over thesubstrate prior to UV-radiation curing which is accomplished by exposingthe molten film to UV-radiation and the crosslinking reactions aretriggered with UV-radiation rather than heat. Thus, powder coating heatsensitive substrates with UV-radiation curable powders requires a twostep process typically comprising the steps of: i) heating the powdercoating composition to melt and flow it out onto the substrate in orderto form a continuous film, and ii) UV radiate the film formed in orderto harden (cure) it. In principle, heat curing of heat sensitivesubstrates is still desirable and preferred over UV curing; the reasonis that heat curing has the advantage that in only a one step processthat of heating a powder coating composition without the use ofadditional equipment, for instance equipment that generates UV light oraccelerated electrons, the powder coating composition can be melted andcured onto a substrate.

Heat curing of thermosetting powder coating compositions is furtherdesirable over UV curing because UV curing fails when it comes to powdercoat complex three-dimensional articles and heat curing is the only waythat powder coating of complex three-dimensional articles can beaccomplished.

A drawback of thermosetting powder coating compositions comprisingthermal radical initiators and resins comprising unsaturations based oncarbon carbon double bonds connected directly to an electron withdrawinggroup is that due to their generally high reactivity, their physicalstorage stability is rather limited; this drawback is especiallypronounced for prolonged storage such as several weeks; prolongedstorage conditions are typically encountered during for example overseasshipping of powders is rather limited; in these conditions, said powdersneed to be stored at rather low temperatures typically lower than 15°C.; limited/poor physical storage stability apart from adding to thecomplexity of commercializing such a powder due to special requirementsfor storage, it is generally undesirable by the paint manufacturer andthe end user alike, since limited/poor physical storage stability ofpowder paints results to block or sinter during storage and/or producingan aesthetically undesirable orange peel finish when cured.

The complexity of the task to develop thermosetting powder coatingcompositions having high physical storage stability and at the same timesaid thermosetting powder coating compositions being able to produceupon heat-curing at low temperatures powder coatings having enhanced,preferably significantly enhanced chemical resistance becomes ever morecomplex once one wishes to also enhance the speed of heat-curing at lowtemperatures. The faster the heat-curing of a thermosetting powdercoating composition at a low temperature, that is the shorter the time athermosetting powder coating composition requires to produce a powdercoating having an acceptable chemical resistance upon said compositionbeen heat-cured at low temperatures, the better it is. The reason beinga thermosetting powder coating composition which can heat-cure fast atlow temperatures offers to the powder coating applicator fastturn-around time due to the fact that he can handle the coated articlesat significant shorter times after coating the articles without riskingdamaging their coated surfaces and at the same time offers him theopportunity to also coat heat-sensitive articles apart fromnon-heat-sensitive articles. The complexity of this task becomes evenmore complex once one wishes that said thermosetting powder coatingcomposition is able to produce upon fast heat-cure at low temperaturespowder coatings which have sufficient smoothness. The smoothnessconcerns the finish of a powder coating and it is particularly importantfor the aesthetic attractiveness of a powder coated article for theend-consumer.

In recent years, heat curable powder coating compositions that can becured at low temperatures were proposed in WO 2010/052290, WO2010/052291, WO 2010/052293, WO 2011/138431, WO 2011/138432, WO2014/173861, and WO 2015/075186. However, none of those disclosures wasable to provide for heat curable thermosetting powder coatingcompositions which would be able to heat-cure fast at low temperature(as this is defined herein) and none of those disclosures was able toprovide for heat curable thermosetting powder coating compositions thatupon heat-curing at low temperature would be able to produce powdercoatings having at least good, preferably very good, more preferablyexcellent chemical resistance.

It would thus, be desirable and is, therefore, the primary object of theinvention to provide heat curable thermosetting powder coatingcompositions which are able to heat-cure fast at low temperature andsaid heat curable thermosetting powder coating compositions uponheat-curing at low temperature are able to produce powder coatingshaving at least good, preferably very good, more preferably excellentchemical resistance. It would be further desirable and is, thereforeanother object of the invention to provide heat curable thermosettingpowder coating compositions which are able to heat-cure fast at lowtemperature, have very good physical storage stability and said heatcurable thermosetting powder coating compositions upon heat-curing atlow temperature are able to produce powder coatings having at leastgood, preferably very good, more preferably excellent chemicalresistance. It would be further desirable and is, therefore a furtherobject of the invention to provide heat curable thermosetting powdercoating compositions which are able to heat-cure fast at lowtemperature, have very good physical storage stability, and said heatcurable thermosetting powder coating compositions upon heat-curing atlow temperature are able to produce powder coatings having: i) at leastgood, preferably very good, more preferably excellent chemicalresistance, and ii) at least sufficient smoothness.

Therefore, broadly in accordance with the invention there is provided athermosetting powder coating composition as disclosed herein and asdescribed in the claims. More particularly, the invention is asdisclosed herein and as described in the claims.

DETAILED DESCRIPTION

It was surprisingly found that the thermosetting powder coatingcomposition (TPCC) of the invention are heat curable and are able toheat-cure fast at low temperature and said heat curable thermosettingpowder coating compositions upon heat-curing at low temperature are ableto produce powder coatings having at least good, preferably very good,more preferably excellent chemical resistance. Thus, the TPCC of theinvention meet the primary object of the invention. Preferably, the TPCCof the invention are able to heat-cure fast at low temperature, havevery good physical storage stability and said heat curable thermosettingpowder coating compositions upon heat-curing at low temperature are ableto produce powder coatings having at least good, preferably very good,more preferably excellent chemical resistance. More preferably, the TPCCof the invention are able to heat-cure fast at low temperature, havevery good physical storage stability, and said heat curablethermosetting powder coating compositions upon heat-curing at lowtemperature are able to produce powder coatings having: i) at leastgood, preferably very good, more preferably excellent chemicalresistance, and ii) at least sufficient smoothness. Most preferably theTPCC of the invention are able to heat-cure fast at low temperature,have very good physical storage stability, and said heat curablethermosetting powder coating compositions upon heat-curing at lowtemperature are able to produce powder coatings having: i) at leastgood, preferably very good, more preferably excellent chemicalresistance, and ii) at least sufficient smoothness; and said heatcurable thermosetting powder coating compositions may be also able toheat-cure at very low temperature and upon heat-curing at very lowtemperature are able to produce powder coatings having: i) at leastsufficient, preferably good, more preferably very good, most preferablyexcellent chemical resistance.

Hence, broadly in accordance with the invention, there is provided athermosetting powder coating composition as described in the claims andas disclosed herein.

Broadly in accordance with the invention, there is provided a curedcomposition as described in the claims and as disclosed herein.

Broadly in accordance with the invention, there is provided an articleas described in the claims and as disclosed herein.

Broadly in accordance with the invention, there are provided varioususes as described in the claims and as disclosed herein.

P1a More particularly broadly in accordance with the invention there isprovided a thermosetting powder coating composition comprising thefollowing components A to C:

-   -   A: one or more unsaturated resins comprising ethylenic        unsaturations (UR) selected from the group consisting of        polyester resins, acrylic resins, polyurethanes, epoxy resins,        polyamides, polyesteramides, polycarbonates, polyureas and        mixtures thereof, and    -   B: one or more curing agents selected from the group consisting        of vinyl urethanes, vinyl functionalized urethane resins and        mixtures thereof, wherein at least one curing agent is curing        agent A which is selected from the group consisting of i), ii)        and iii):        -   i) one or more crystalline VU-c each of which is a            crystalline vinyl urethane having a melting enthalpy            ΔH_(m)≥35 J/g, and one or more melting temperatures (T_(m))            wherein any and all of the T_(m) of the one or more            crystalline VU-c are in the region of from and including 30            up to and including 80° C., and        -   ii) one or more crystalline VFUR-c each of which is a            crystalline vinyl functionalized urethane resin having a            melting enthalpy ΔH_(m)≥35 J/g, and one or more melting            temperatures (T_(m)) wherein any and all of the T_(m) of the            one or more crystalline VFUR-c are in the region of from and            including 30 up to and including 80° C., and        -   iii) mixtures of crystalline VU-c and crystalline VFUR-c,    -   wherein the ΔH_(m) and T_(m) is each measured via Differential        Scanning Calorimetry (DSC) according to the description, and    -   C: one or more thermal radical initiators, wherein at least one        thermal radical initiator is peroxydicarbonate-X which is        present in an amount of at least 26 and at most 500 mmol/Kg A        and B, and wherein the peroxydicarbonate-X is selected from the        group consisting of peroxydicarbonates represented by the        following formula X, and mixtures thereof,

-   -   wherein R₁ is C₉-C₂₂ saturated hydrocarbyl, and R₂ is C₉-C₂₂        saturated hydrocarbyl.

P1b More specifically broadly in accordance with the invention there isprovided a thermosetting powder coating composition according to claim1.

Certain dependent exemplary preferments of the thermosetting powdercoating composition according to P1a, P1b, as well as certain furtheraspects of the invention of the thermosetting powder coating compositionaccording to P1a, P1b, and their preferments include but are not limitedto preferments P1 to P112 and aspects A1 to A7, shown below. Many othervariations, combinations and embodiments of the invention will beapparent to those skilled in the art and such variations, combinationsand embodiments are contemplated within the scope of the claimedinvention. The antecedent basis for certain terms shown in thepreferments can be found in preceding preferments and/or in any one ofP1a and P1b. Any reference to components includes their preferments andpreferred ranges as disclosed in the entire application.

P1 The thermosetting powder coating composition according to any one ofP1a and P1b, wherein the peroxydicarbonate-X is selected from the groupconsisting of peroxydicarbonates represented by the following formula X,and mixtures thereof,

wherein the R₁ is a C₁₀-C₁₈ saturated hydrocarbyl, and the R₂ is aC₁₀-C₁₈ saturated hydrocarbyl.

P2 The thermosetting powder coating composition according to any one ofP1a and P1b, the peroxydicarbonate-X is selected from the groupconsisting of peroxydicarbonates represented by the following formula X,and mixtures thereof,

wherein the R₁ is a C₁₀-C₁₆ saturated hydrocarbyl, and the R₂ is aC₁₀-C₁₆ saturated hydrocarbyl.

P3 The thermosetting powder coating composition according to any one ofP1a and P1b, wherein the peroxydicarbonate-X is selected from the groupconsisting of dimyristyl peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate, and mixtures thereof.

P4 The thermosetting powder coating composition according to any one ofP1a and P1b, wherein the peroxydicarbonate-X is selected from the groupconsisting of di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetylperoxydicarbonate, and mixtures thereof.

P5 The thermosetting powder coating composition according to any one ofP1a and P1b, wherein the peroxydicarbonate-X is dicetylperoxydicarbonate.

P6 The thermosetting powder coating composition according to any one ofP1a and P1b, wherein the peroxydicarbonate-X isdi(4-tert-butylcyclohexyl) peroxydicarbonate.

P7 The thermosetting powder coating composition according to any one ofP1a and P1b, wherein the peroxydicarbonate-X is dimyristylperoxydicarbonate.

P8 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P7, wherein B ispresent in an amount of at least 4 and at most 90, more preferably in anamount of at least 10 and at most 85, even more preferably in an amountof at least 15 and at most 60, most preferably in an amount of at least15 and at most 55, especially in an amount of at least 16 and at most 55pph of A and B.

P9 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P8, wherein thecuring agent A is present in an amount of at least 5, more preferably atleast 10, even more preferably at least 20, most preferably at least 30,especially at least 40, more especially at least 50, most especially atleast 60, for example at least 70, for example at least 80, for exampleat least 90, for example at least 94, for example at least 95, forexample at least 96, for example at least 97, for example at least 98,for example at least 99, for example at least 99.1, for example at least99.2, for example at least 99.3, for example at least 99.4, for exampleat least 99.5, for example at least 99.6, for example at least 99.7, forexample at least 99.8, for example at least 99.9, for example 100 pph ofB.

P10 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P9, wherein B: oneor more curing agents selected from the group consisting of vinylurethanes, vinyl functionalized urethane resins and mixtures thereof,wherein any and all of the curing agents is curing agent A as curingagent A is disclosed in any one of P1a and P1b, or in any one ofsections 1.2, 1.2.1 and 1.2.2, including any preferred range andcombinations of said preferred ranges.

P11 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P9, wherein B: oneor more curing agents A as curing agent A is disclosed in any one of P1aand P1b, or in any one of sections 1.2, 1.2.1 and 1.2.2, including anypreferred range and combinations of said preferred ranges.

P12 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P11, wherein the Kbeing the ratio of the total mol of the ethylenic unsaturations in Bdivided to the total mol of the ethylenic unsaturations in A, is atleast 0.3 and at most 9, more preferably at least 0.5 and at most 4,most preferably at least 0.6 and at most 3, especially at least 0.8 andat most 2.8, more especially at least 0.9 and at most 2.6, mostespecially at least 0.95 and at most 2.5, for example at least 0.95 andat most 3, for example at least 0.8 and at most 2.5.

P13 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho compounds, and mixtures thereof.

P14 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho compounds, and mixtures thereof, and whereinthe total amount of component D is as disclosed in section 1.4 includingany preferred range and combinations of said preferred ranges.

P15 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho compounds, and mixtures thereof, wherein theonium compounds are selected from any group consisting of prefermentsdisclosed in section 1.4 and/or 1.4.1 concerning the onium compounds,and the sulpho compounds are selected from any group consisting ofpreferments disclosed in section 1.4 and/or 1.4.2 concerning the sulphocompounds.

P16 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho compounds, and mixtures thereof, wherein theonium compounds are selected from any group consisting of prefermentsdisclosed in section 1.4 and/or 1.4.1 concerning the onium compounds,and the sulpho compounds are selected from any group consisting ofpreferments disclosed in section 1.4 and/or 1.4.2 concerning the sulphocompounds, and wherein the total amount of component D is as disclosedin section 1.4 including any preferred range and combinations of saidpreferred ranges.

P17 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

P18 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, sulpho-compound-3,and sulpho-compound-5.

P19 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, andsulpho-compound-3.

P20 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-2, and sulpho-compound-3.

P21 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-3.

P22 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, and compoundsrepresented by formula VIII-X; and wherein the sulpho-compounds areselected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, sulpho-compound-4, andsulpho-compound-5.

P23 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, and compounds represented by formula VII-X; and whereinthe sulpho-compounds are selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4, and sulpho-compound-5.

P24 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaV-X, compounds represented by formula VI-X, and compounds represented byformula VII-X; and wherein the sulpho-compounds are selected from thegroup consisting of sulpho-compound-1, sulpho-compound-2,sulpho-compound-3, sulpho-compound-4, and sulpho-compound-5.

P25 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula V-X, compounds represented by formulaVI-X, and compounds represented by formula VII-X; and wherein thesulpho-compounds are selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

P26 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula V-X, compounds represented by formulaVI-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

P27 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula V-X; and wherein the sulpho-compoundsare selected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, sulpho-compound-4 andsulpho-compound-5.

P28 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X; andwherein the sulpho-compounds are selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

P29 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula II-X; and wherein the sulpho-compounds areselected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, sulpho-compound-4 andsulpho-compound-5.

P30 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula II-X; and wherein the sulpho-compounds areselected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, and sulpho-compound-5.

P31 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, and compounds represented by formula II-X;and wherein the sulpho-compounds are selected from the group consistingof sulpho-compound-1, sulpho-compound-2, and sulpho-compound-3.

P32 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, and compounds represented by formula II-X;and wherein the sulpho-compounds are selected from the group consistingof sulpho-compound-2, and sulpho-compound-3.

P33 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, and compounds represented by formula II-X;and wherein the sulpho-compounds are selected from the group consistingof sulpho-compound-3.

P34 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X; and compounds represented by formula II-X.

P35 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds wherein the onium compounds are selected from thegroup consisting of compounds represented by formula II-X.

P36 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X and compounds represented by formula II-X andwherein the A⁻ in formulae I-X and II-X is selected from the groupconsisting of halide anions, perhalide anions, phosphate anions,arsenate anions, antimonite anions, sulphonate anions, and borateanions.

P37 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X and compounds represented by formula II-X andwherein the A⁻ in formulae I-X and II-X is selected from the group ofhalide anions, perhalide anions, phosphate anions, sulphonate anions,and borate anions.

P38 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof onium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X and compounds represented by formula II-X andwherein the A⁻ in formulae I-X and II-X is selected from the group ofhalide anions.

P39 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfinate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate, triethylsulfonium tetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,pentan-3-one O-tosyl oxime, (E)-3,4-dihydronaphthalen-1(2H)-oneO-((4-chlorophenyl)sulfonyl) oxime and mixtures thereof.

P40 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate, triethylsulfonium tetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,(E)-3,4-dihydronaphthalen-1 (2H)-one O-((4-chlorophenyl)sulfonyl) oximeand mixtures thereof.

P41 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate, triethylsulfonium tetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P42 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P43 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P44 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-ethoxy-2-methylpyridinium hexafluorophosphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate, tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P45 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate, tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P46 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P47 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P48 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P49 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

P50 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate, and mixtures thereof.

P51 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, tert-butyl4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate, and mixtures thereof.

P52 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, tert-butyl4-methylbenzenesulfonate, and mixtures thereof.

P53 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P54 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P55 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P56 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-dodecylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P57 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P58 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium p-toluene sulphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P59 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium p-toluene sulphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P60 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P61 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

P62 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

P63 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

P64 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof bis(4-tert-butylphenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

P65 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, diphenyliodonium chloride, diphenyliodoniumhexafluorphosphate, diphenyliodonium p-toluene sulphate, and mixturesthereof.

P66 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, diphenyliodonium chloride, diphenyliodoniumhexafluorphosphate, and mixtures thereof.

P67 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof diphenyliodonium chloride, diphenyliodonium hexafluorphosphate, andmixtures thereof.

P68 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D: one or more co-initiators selected from the group consistingof diphenyliodonium chloride,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanoneand mixtures thereof.

P69 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P12, wherein thethermosetting powder coating composition further comprises component D,wherein D is diphenyliodonium chloride.

P70 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P92, wherein thethermosetting powder coating composition further comprises component D,wherein the component D is present in an amount of at most 95 mmol/Kg Aand B.

P71 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P92, wherein thethermosetting powder coating composition further comprises component D,wherein the component D is present in an amount of at least 1 and atmost 95, more preferably at least 5 and at most 95, even more preferablyat least 10 and at most 95 mmol/Kg A and B.

P72 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P71, wherein thethermosetting powder coating composition further comprises component E,wherein E: one or more inhibitors.

P73 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P71, wherein thethermosetting powder coating composition further comprises component E,wherein E: one or more inhibitors and wherein the total amount ofcomponent E is as disclosed in section 1.5 including any preferred rangeand combinations of said preferred ranges.

P74 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P71, wherein thethermosetting powder coating composition further comprises component E,wherein E: one or more inhibitors selected from any group consisting ofpreferments disclosed in section 1.5.

P75 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P71, wherein thethermosetting powder coating composition further comprises component E,wherein E: one or more inhibitors selected from any group consisting ofpreferments disclosed in section 1.5, and wherein the total amount ofcomponent E is as disclosed in section 1.5 including any preferred rangeand combinations of said preferred ranges.

P76 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P71, wherein thethermosetting powder coating composition further comprises component E,wherein E: one or more inhibitors selected from the group consisting ofphenolic compounds, stable radicals, catechols, phenothiazines,hydroquinones, benzoquinones and mixtures thereof.

P77 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P71, wherein thethermosetting powder coating composition further comprises component E,wherein E: one or more inhibitors selected from the group consisting ofphenolic compounds, stable radicals, catechols, phenothiazines,hydroquinones, benzoquinones and mixtures thereof, and wherein the totalamount of component E is as disclosed in section 1.5 including anypreferred range and combinations of said preferred ranges.

P78 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P72 to P77, wherein thecomponent E is present in an amount of at least 16 and at most 1500,more preferably at least 20 and at most 1500, even more preferably atleast 16 and at most 1000, most preferably at least 20 and at most 1000,especially at least 16 and at most 800, more especially at least 20 andat most 800, most especially at least 16 and at most 600, for example atleast 20 and at most 600, for example at least 25 and at most 800, forexample at least 30 and at most 800, for example at least 40 and at most1500, for example at least 40 and at most 1000, for example at least 40and at most 800, for example at least 40 and at most 700, for example atleast 40 and at most 600, for example at least 40 and at most 500, forexample at least 45 and at most 1500, for example at least 45 and atmost 1000, for example at least 45 and at most 800, for example at least45 and at most 700, for example at least 45 and at most 600, for exampleat least 45 and at most 500, for example at least 45 and at most 300mg/Kg A and B.

P79 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P78, wherein theperoxydicarbonate-X is present in an amount of at least 30, preferablyat least 40, more preferably at least 45 mmol/Kg A and B.

P80 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P79, wherein theperoxydicarbonate-X is present in an amount of at most 500, preferablyat most 400, more preferably at most 350, even more preferably at most300, most preferably at most 250 mmol/Kg A and B.

P81 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P78, wherein theperoxydicarbonate-X is present in an amount of at least 45 and at most250 mmol/Kg A and B.

P82 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P80, wherein theperoxydicarbonate-X is present in an amount of at least 30 and at most500, more preferably of at least 35 and at most 500, even morepreferably of at least 40 and at most 500, most preferably of at least45 and at most 500, especially of at least 26 and at most 450, moreespecially of at least 30 and at most 450, most especially of at least35 and at most 450, for example of at least 40 and at most 450, forexample of at least 45 and at most 450, for example of at least 26 andat most 400, for example of at least 30 and at most 400, for example ofat least 35 and at most 400, for example of at least 40 and at most 400,for example of at least 45 and at most 400, for example of at least 26and at most 350, for example of at least 30 and at most 350, for exampleof at least 35 and at most 350, for example of at least 40 and at most350, for example of at least 45 and at most 350, for example of at least26 and at most 300, for example of at least 30 and at most 300, forexample of at least 35 and at most 300, for example of at least 40 andat most 300, for example of at least 45 and at most 300, for example ofat least 26 and at most 250, for example of at least 30 and at most 250,for example of at least 35 and at most 250, for example of at least 40and at most 250, for example of at least 45 and at most 250 mmol/Kg Aand B.

P83 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P82, wherein thecomponent C comprises peroxydicarbonate-X in an amount of at least 5.2,more preferably of at least 6, even more preferably of at least 7, mostpreferably of at least 8, especially of at least 9, more especially ofat least 9.6, even more especially of at least 10.4, most especially ofat least 12, for example of at least 14, for example of at least 16, forexample of at least 18, for example of at least 19.2, for example of atleast 20, for example of at least 25, for example of at least 30, forexample of at least 40, for example of at least 50, for example of atleast 60, for example of at least 70, for example of at least 80 forexample of at least 90 for example of at least 95 for example of atleast 96, for example of at least 97, for example of at least 98, forexample of at least 99, for example of at least 99.5, for example atleast 99.9 pph of C, for example the component C is peroxydicarbonate-X.

P84 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P83, wherein thetotal amount of the component C is at most 500, preferably at most 450,more preferably at most 400, even more preferably at most 350,especially at most 300, more especially at most 250 mmol/Kg A and B.

P85 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P84, wherein each ofthe UR has a number average molecular weight (M_(n)) measured via GelPermeation Chromatography (GPC) according to the description, of atleast 1000 and at most 10000 Da.

P86 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P85, wherein each ofthe UR has a glass transition temperature (T_(g)) measured via DSCaccording to the description, of from and including 40 up to andincluding 80° C., preferably of from and including 40 up to andincluding 75° C.

P87 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P86, wherein the URhas a weight per unsaturation (WPU) measured via ¹H-NMR spectroscopy, ofat least 250 and at most 2200, preferably from 450 to 1350 g/mol.

P88 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P87, wherein each ofthe crystalline VU-c and each of the crystalline VFUR-c has a numberaverage molecular weight (M_(n)) measured via Gel PermeationChromatography (GPC) according to the description, of at least 400 andof at most 20000 Da, more preferably of at least 450 and of at most10000 Da, most preferably of at least 500 and of at most 7000 Da,especially of at least 550 and of at most 5000, more especially of atleast 575 and of at most 3000 Da, most especially of at least 600 and ofat most 2000 Da, for example of at least 660 and of at most 2000 Da, forexample of at least 660 and of at most 1500 Da, for example of at least660 and of at most 1200 Da, for example of at least 660 and of at most1000 Da.

P89 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P88, wherein any andall of the T_(m) of the one or more crystalline VU-c, are in the regionof from and including 45 up to and including 78° C., preferably in theregion of from and including 45 up to and including 77° C.

P90 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P89, wherein any andall of the T_(m) of each of the one or more crystalline VFUR-c, are inthe region of from and including 45 up to and including 78° C.,preferably in the region of from and including 45 up to and including77° C.

P91 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P90, wherein whereineach of the crystalline VU-c and each of the crystalline VFUR-c has amelting enthalpy ΔH_(m)≥60, preferably ≥100, more preferably ≥120 J/g.

P92 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P91, wherein each ofthe crystalline VU-c has a weight per unsaturation (WPU) measured via¹H-NMR spectroscopy according to the description, of at least 190 and atmost 1500 g/mol, preferably of at least 190 and at most 1000 g/mol, morepreferably of at least 190 and at most 800 g/mol, most preferably of atleast 190 and at most 600 g/mol, especially of at least 190 and at most500 g/mol, more especially of at least 190 and at most 350 g/mol.

P93 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P92, wherein each ofthe crystalline VFUR-c has a weight per unsaturation (WPU) measured via¹H-NMR spectroscopy according to the description, of at least 190 and atmost 1500 g/mol, preferably of at least 190 and at most 1000 g/mol, morepreferably of at least 190 and at most 800 g/mol, even more preferablyof at least 190 and at most 600 g/mol, most preferably of at least 190and at most 500 g/mol, especially of at least 190 and at most 350 g/mol.

P94 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P93, wherein thecrystalline VU-c is selected from the group consisting of crystallineVEU-c, crystalline VESU-c, VEESU-c, and mixtures thereof’; preferablythe crystalline VU-c is selected from the group consisting ofcrystalline VEU-c; more preferably the crystalline VU-c is selected fromthe group consisting of diethylene glycol divinyl ether urethane,triethylene glycol divinyl ether urethane, and mixtures thereof; evenmore preferably the crystalline VU-c is diethylene glycol divinyl etherurethane; most preferably the crystalline VU-c is triethylene glycoldivinyl ether urethane.

P95 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P94, wherein thecrystalline VFUR-c is selected from the group consisting of crystallineVEFUR-c, crystalline VESFUR-c, VEESFUR-c, and mixtures thereof;preferably the crystalline VFUR-c is selected from the group consistingof crystalline VEFUR-c, crystalline VESFUR-c, and mixtures thereof; morepreferably the crystalline VFUR-c is selected from the group consistingof crystalline VEFUR-c.

P96 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P95, wherein thecuring agent A is selected from the group consisting of crystalline VU-cand mixtures thereof; preferably the curing agent A is selected from thegroup consisting of crystalline VEU-c, crystalline VESU-c, VEESU-c, andmixtures thereof; more preferably the curing agent A is selected fromthe group consisting of crystalline VEU-c; even more preferably thecuring agent A is selected from the group consisting of diethyleneglycol divinyl ether urethane, triethylene glycol divinyl etherurethane, and mixtures thereof; most preferably the curing agent A isdiethylene glycol divinyl ether urethane; especially the curing agent Ais triethylene glycol divinyl ether urethane.

P97 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P96, wherein the URis selected from the group consisting of polyester resins,polyurethanes, polyamides, polyesteramides, polyureas and mixturesthereof.

P98 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P97, wherein theethylenic unsaturations of the UR are di-acid ethylenic unsaturations.

P99 The thermosetting powder coating composition according to any one ofP1a and P1b, or to any one of the preferments P1 to P96, wherein the URis an unsaturated polyster resin comprising ethylenic unsaturations.

P100 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P96, wherein theUR is an unsaturated polyster resin comprising di-acid ethylenicunsaturations.

P101 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P96, wherein theUR is an unsaturated polyster resin comprising 2-butenedioic acidethylenic unsaturations.

P102 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P101, wherein thecuring agent A has a T_(c) which is lower than its T_(m) and preferablythe T_(c) of the curing agent is at most 55, more preferably at most 50,even more preferably at most 45, most preferably at most 40, especiallyat most 35° C., lower than its T_(m), or lower than its highest T_(m) ifthe curing agent A has more than one T_(m).

P103 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P102, wherein thecuring agent A has a T_(c) of at least 0 and of at most 75, morepreferably of at least 10 and of at most 75, even more preferably of atleast 10 and at most 72, most preferably of at least 10 and at most 70,especially of at least 10 and at most 68, more especially of at least 10and at most 66, for example of at least 10 and at most 65, for exampleof at least 15 and at most 62, for example of at least 20 and at most60° C.

P104 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P103, wherein D:one or more co-initiators selected from the group consisting of oniumcompounds, sulpho-compounds, and mixtures thereof, and wherein the oniumcompounds are selected from the group consisting of compoundsrepresented by the following formula I-X and compounds represented bythe following formula II-X

whereinA⁻ is selected from the group consisting of halide anions; andR₁′″ is a C₁-C₁₂ saturated hydrocarbyl, and R₂′″ is a C₁-C₁₂ saturatedhydrocarbyl.

P105 The thermosetting powder coating composition according to any oneof P1a and P1b, or any one of the preferments P1 to P104, wherein the URhas:

-   -   a) a number average molecular weight (M_(n)) of at least 1000        and at most 10000 Da, and    -   b) a glass transition temperature (T_(g)) of at least 40 and at        most 75° C., and    -   c) a weight per unsaturation (WPU) of at least 250 and at most        2200 g/mol, and wherein the M_(n) is measured via Gel Permeation        Chromatography (GPC) according to the description, the T_(g) is        measured via Differential Scanning Calorimetry (DSC) according        to the description and the WPU is measured via ¹H-NMR        spectroscopy according to the description.

P106 The thermosetting powder coating composition according to any anyone of P1a and P1b, or any one of the preferments P1 to P105, whereinthe curing agent A which is selected from the group consisting of i),ii) and iii):

-   -   i) one or more crystalline VU-c each of which is a crystalline        vinyl urethane having a melting enthalpy ΔH_(m)≥35 J/g, and one        or more melting temperatures (T_(m)) wherein any and all of the        T_(m) of the one or more crystalline VU-c are in the region of        from and including 45 up to and including 77° C., and a number        average molecular weight (M_(n)) of at least 660 and at most        1200 Da, and    -   ii) one or more crystalline VFUR-c each of which is a        crystalline vinyl functionalized urethane resin having a melting        enthalpy ΔH_(m)≥35 J/g, and one or more melting temperatures        (T_(m)) wherein any and all of the T_(m) of the one or more        crystalline VFUR-c are in the region of from and including 45 up        to and including 77° C., and a number average molecular weight        (M_(n)) of at least 660 and at most 1200 Da, and    -   iii) mixtures of crystalline VU-c and crystalline VFUR-C,        wherein the M_(n) is measured via Gel Permeation Chromatography        (GPC) according to the description.

P107 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P106, wherein thecrystalline VFUR-c has a T_(g) of at least −80 and at most 75° C., morepreferably of at least −80 and at most 70° C., even more preferably ofat least −80 and at most 60° C., most preferably of at least −80 and atmost 50° C., especially of at least −80 and at most 40° C., moreespecially of at least −80 and at most 30° C., most especially of atleast −80 and at most 20° C., for example of at least −80 and at most10° C., for example of at least −80 and at most 0° C., for example of atleast −80 and at most −10° C., for example of at least −80 and at most−20° C.

P108 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P107, wherein theUR has a glass transition temperature (T_(g)) of at least 20 and at most120, more preferably of at least 30 and at most 100, even morepreferably of at least 35 and at most 90, most preferably of at least 40and at most 75° C.

P109 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P108, wherein thethermosetting powder coating composition of the invention has a glasstransition temperature of at least 20 and at most 80, more preferably atleast 25 and at most 70, even more preferably at least 25 and at most60, most preferably at least 25 and at most 55, especially at least 25and at most 50, more especially at least 30 and most 80, even moreespecially at least 30 and at most 70, most especially at least 30 andat most 60, for example at least 30 and at most 55, for example at least30 and at most 50° C.

P110 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P109, wherein thethermosetting powder coating composition is a one componentthermosetting powder coating composition.

P111 The thermosetting powder coating composition according to any oneof P1a and P1b, or to any one of the preferments P1 to P110.

P112 The thermosetting powder coating composition according to any oneof the claims presented herein and any one of the preferments P1 toP111.

A1 A process for making a thermosetting powder coating composition asdefined in any one of any one of P1a and P1b, or in any one of thepreferments P1 to P112, said process comprising the steps of:

-   -   a. mixing the components of the thermosetting powder coating        composition to obtain a premix;    -   b. heating the premix preferably in an extruder, preferably up        to and including the decomposition temperature of the component        C, more preferably up to and including 85° C., to obtain an        extrudate;    -   c. cooling down the extrudate to obtain a solidified extrudate;        and    -   d. grinding the solidified extrudate into smaller particles to        obtain the thermosetting powder coating composition.

A2 A cured thermosetting powder coating composition obtained by curing athermosetting powder coating composition as defined in any one of anyone of P1a and P1b, or in any one of the preferments P1 to P112.

A3 An article having coated thereon a thermosetting powder coatingcomposition as defined in any one of any one of P1a and P1b, or in anyone of the preferments P1 to P112.

A4 An article having coated and cured thereon a thermosetting powdercoating composition as defined in any one of any one of P1a and P1b, orin any one of the preferments P1 to P112.

A5 A process for making a coated article, said process comprising thesteps of:

-   -   applying a thermosetting powder coating composition as defined        in any one of any one of P1a and P1b, or in any one of the        preferments P1 to P112, to an article; and    -   heating and/or radiating the thermosetting powder coating        composition for enough time and at a suitable temperature to        cure the thermosetting powder coating composition, to obtain the        coated article.

A6 Use of:

-   -   a thermosetting powder coating composition as defined in any one        of any one of P1a and P1b, or in any one of the preferments P1        to P112; or    -   a cured thermosetting powder coating composition as defined in        aspect A2; or    -   an article as defined in any one of aspects A3 to A4, in powder        coatings, powder coatings for heat-sensitive articles, powder        coatings for non-heat-sensitive articles, 3D-printing,        automotive applications, marine applications, aerospace        applications, medical applications, defense applications,        sports/recreational applications, architectural applications,        bottling applications, household applications, machinery        applications, can applications, coil applications, energy        applications, textile applications and electrical applications.

A7 A process for making either powder coatings, or powder coatings forheat-sensitive articles, or powder coatings for non-heat-sensitivearticles, or compositions suitable for 3D-printing, or compositionssuitable for applications selected from the group consisting ofautomotive applications, marine applications, aerospace applications,medical applications, defense applications, sports/recreationalapplications, architectural applications, bottling applications,household applications, machinery applications, can applications, coilapplications, energy applications, textile applications and electricalapplications, or articles suitable for applications selected from thegroup consisting of automotive applications, marine applications,aerospace applications, medical applications, defense applications,sports/recreational applications, architectural applications, bottlingapplications, household applications, machinery applications, canapplications, coil applications, energy applications, textileapplications and electrical applications, comprising the step ofproviding at least one of the following i) to iii):

-   -   i) a thermosetting powder coating composition as defined in any        one of P1a and P1b, or in any one of the preferments P1 to P112,    -   ii) a cured thermosetting powder coating composition as defined        in aspect A2,    -   iii) an article as defined in any one of aspects A3 to A4.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in any oneof the preferments P1 to P112 and aspects A1 to A7, shown below can becombined with each other and with any other feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects of the invention as these are disclosed in the entireapplication.

Definitions

By ‘peroxydicarbonate’ is meant an organic peroxide comprising thefollowing group: . . . —C—O—C(═O)—O—O—C(═O)—O—C— . . . . Aperoxydicarbonate is an example of an organic peroxide and thus also anexample of a thermal radical initiator.

The ‘peroxydicarbonate-X’ is selected from the group consisting ofperoxydicarbonates represented by the following formula X, and mixturesthereof,

wherein R₁ is a C₉-C₂₂ saturated hydrocarbyl, and R₂ is a C₉-C₂₂saturated hydrocarbyl; preferably the R₁ is a C₁₀-C₁₈ saturatedhydrocarbyl, and R₂ is a C₁₀-C₁₈ saturated hydrocarbyl; more preferablythe R₁ is a C₁₀-C₁₆ saturated hydrocarbyl, and R₂ is a C₁₀-C₁₆ saturatedhydrocarbyl; even more preferably, the peroxydicarbonate-X is selectedfrom the group consisting of dimyristyl peroxydicarbonate,di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate,and mixtures thereof; most preferably, the peroxydicarbonate-X isselected from the group consisting of di(4-tert-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate, and mixtures thereof;especially the peroxydicarbonate-X is dimyristyl peroxydicarbonate; moreespecially the peroxydicarbonate-X is di(4-tert-butylcyclohexyl)peroxydicarbonate; most especially the peroxydicarbonate-X is dicetylperoxydicarbonate.

By ‘dimyristyl peroxydicarbonate’ is meant the peroxydicarbonate havingthe following formula:

By ‘di(4-tert-butylcyclohexyl) peroxydicarbonate’ is meant theperoxydicarbonate having the following formula:

By ‘dicetyl peroxydicarbonate’ is meant the peroxydicarbonate having thefollowing formula:

By the term ‘hydrocarbon’ is meant a chemical compound consisting ofcarbon and hydrogen only.

By the term ‘saturated hydrocarbon’ is meant that the hydrocarbon doesnot contain any cis- or trans-configured carbon-carbon double bond(carbon-carbon double bond unsaturation), and it does not contain acarbon-carbon triple bond (carbon-carbon triple bond unsaturation).

By the term ‘unsaturated hydrocarbon’ is meant that the hydrocarbon hasat least one carbon-carbon double bond and no carbon-carbon triple bond.

By the term ‘hydrocarbyl’ is meant a univalent organic group formed byremoving a hydrogen atom from a saturated or unsaturated hydrocarbon.Exemplary hydrocarbyls include but are not limited to methyl, ethyl,phenyl, benzyl, methylphenyl.

By the term ‘saturated hydrocarbyl’ is meant a univalent organic groupformed by removing a hydrogen atom from a saturated hydrocarbon.Exemplary hydrocarbyls include but are not limited to methyl, ethyl,propyl.

By the term ‘hydrocarbylene’ is meant a divalent organic group formed byremoving two hydrogen atoms from a saturated or unsaturated hydrocarbon,the free valences of which are not engaged in a double bond. Exemplaryhydrocarbylenes include but are not limited to methylene, 1,3-phenylene.

By the term ‘substituted-hydrocarbyl’ is meant a hydrocarbyl optionallysubstituted by one or more substituents.

By the term ‘substituent’ is meant an atom or a group of atoms thatreplaces one or more hydrogen atoms attached to a parent structure.Exemplary substituents include but are not limited to oxygen, chlorine,carboxyl, hydroxyl, amino, cyano, methoxy, formyl, imino, etc.

The ‘co-initiator’ is selected from the group consisting of oniumcompounds, sulpho-compounds, and mixtures thereof.

The ‘onium compound’ is selected from the group consisting of compoundsrepresented by the following formula Y

Q⁺A⁻  (formula Y)

wherein Q⁺ is a cation selected from the group consisting of cations-B,cations-B1 and cations-B2, as each of them is defined below in i) toiii), respectively:

-   -   i) cations-B: these cations are derived by addition of a hydron        (H⁺) to a mononuclear parent hydride of N, P, As, Sb, Bi, O, S,        Se, Te, Po, F, Cl, Br, I, At (preferably of N, P, O, S, and I,        more preferably of N, S, and I, more preferably of S, and I,        even more preferably of I), and    -   ii) cations-B1: these cations are derivatives of the cations-B,        and are formed by substitution of the cations-B by univalent        groups, and    -   iii) cations-B2: these cations are derivatives of the cations-B,        and are formed by substitution of the cations-B by groups having        two or three free valences on the same atom.        and wherein A⁻ is an anion which is the counter-anion to Q⁺, and        wherein A⁻ is selected from the group consisting of halide        anions, perhalide anions, phosphate anions, arsenate anions,        antimonite anions, sulphonate anions, and borate anions.        Preferably, A⁻ is selected from the group consisting of halide        anions, perhalide anions, phosphate anions, arsenate anions,        sulphonate anions, and borate anions. More preferably, A⁻ is        selected from the group consisting of halide anions, perhalide        anions, phosphate anions, sulphonate anions, and borate anions.        Even more preferably, A⁻ is selected from the group consisting        of halide anions, perhalide anions, phosphate anions, and        sulphonate anions. Most preferably, A⁻ is selected from the        group consisting of halide anions, phosphate anions and        sulphonate anions. Especially A⁻ is selected from the group        consisting of halide anions and sulphonate anions. More        especially A⁻ is selected from the group consisting of halide        anions. Even more especially A⁻ is selected from the group        consisting of of F⁻, Cl⁻, Br⁻, and I⁻. Most especially A⁻ is        selected from the group consisting of Cl⁻, and I⁻. For example        A⁻ is Cl⁻.

By the term ‘halide anion’ is meant an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, At⁻. Preferably the halide anion is ananion selected from the group consisting of F⁻, Cl⁻, Br⁻, and I⁻. Morepreferably the halide anion is an anion selected from the groupconsisting of Cl⁻, Br⁻, and I⁻. Even more preferably the halide anion isan anion selected from the group consisting of Cl⁻, and I⁻. Mostpreferably the halide anion is Cl⁻.

By the term ‘perhalide anion’ is meant an anion selected from the groupconsisting of FO₄ ⁻, ClO₄ ⁻, BrO₄ ⁻, IO₄ ⁻. Preferably the perhalideanion is ClO₄ ⁻ (perchlorate anion).

By the term ‘phosphate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula PA

PX⁻  (formula PA)

wherein X is selected from the group consisting of F, Cl, Br, I, At.Preferably the X is selected from the group consisting of F, Cl, Br, andI. More preferably the X is selected from the group consisting of F, Cl,and Br. Even more preferably the X is selected from the group consistingof F, and Cl. Most preferably the X is F. An example of a phosphateanion (and most preferred of the phosphate anions) is PF₆ ⁻.

By the term ‘arsenate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula AA

AsX⁻  (formula AA)

wherein X is selected from the group consisting of F, Cl, Br, I, At.Preferably the X is selected from the group consisting of F, Cl, Br, andI. More preferably the X is selected from the group consisting of F, Cl,and Br. Even more preferably the X is selected from the group consistingof F, and Cl. Most preferably the X is F. An example of an arsenateanion (and most preferred of the arsenate anions) is AsF₆ ⁻.

By the term ‘antimonate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula ATA

SbX⁻  (formula ATA)

wherein X is selected from the group consisting of F, Cl, Br, I, At.Preferably the X is selected from the group consisting of F, Cl, Br, andI. More preferably the X is selected from the group consisting of F, Cl,and Br. Even more preferably the X is selected from the group consistingof F, and Cl. Most preferably the X is F. An example of an antimonateanion (and most preferred of the antimonate anions) is SbF₆ ⁻.

By the term ‘sulphonate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula SA

wherein R₁″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably aC₇-C₁₂ unsaturated hydrocarbyl, more preferably CH₃C₆H₄. Examples ofsulphonate anions include but are not limited to

Preferably the sulphonate anion is selected from the group consisting of1,1,2,2-tetrafluroethanesulphonate anion, perfluoro-1-butanesulphonateanion and p-toluene sulphate anion. More preferably, the sulphonateanion is p-toluene sulphate anion.

By the term ‘borate anion’ is meant an anion selected from the groupconsisting of anions represented by the formula BA, and anionsrepresented by the formula BA-I,

whereinR₂″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆, andR₃″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆, andR₄″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆, andR₅″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆;X is selected from the group consisting of F, Cl, Br, I, At. Preferablythe X is selected from the group consisting of F, Cl, Br, and I. Morepreferably the X is selected from the group consisting of F, Cl, and Br.Even more preferably the X is selected from the group consisting of F,and Cl. Most preferably the X is F.

The ‘sulpho-compound’ is selected from the group consisting ofsulpho-compounds-1, sulpho-compounds-2, sulpho-compounds-3,sulpho-compounds-4, sulpho-compounds-5, and mixtures thereof.

By the term ‘sulpho-compound-1’ is meant a compound represented by thefollowing formula L1

wherein R₁′ is a C₁-C₁₀ hydrocarbyl, and R₂′ is a C₁-C₁₀ hydrocarbyl.Examples of a sulpho-compound-1 include but are not limited to2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane and(diazomethylenedisulfonyl)dicyclohexane.

By the term ‘sulpho-compound-2’ is meant a compound represented by thefollowing formula L2

wherein R₃′ is a C₁-C₁₂ hydrocarbyl, and R₄′ is a C₁-C₁₂ hydrocarbyl.Examples of a sulpho-compound-2 include but are not limited to2-isopropyl-5-methylcyclohexyl 4-methylbenzenesulfonate and cyclohexyl4-methylbenzenesulfonate and cyclohexyl 4-methylbenzenesulfonate.

By the term ‘sulpho-compound-3’ is meant a compound represented by thefollowing formula L3

wherein R₅′ is a C₁-C₁₂ hydrocarbyl, and R₆′ is a C₁-C₁₂ hydrocarbyl andR₇′ is a C₁-C₁₂ saturated hydrocarbyl, and R₈′ is a C₁-C₁₂ saturatedhydrocarbyl. Most preferably, R₅′ is a C₁-C₁₂ hydrocarbyl, and R₆′ is aC₁-C₁₂ hydrocarbyl and R₇′ is CH₃, and R₈′ is CH₃. An example of asulpho-compound-3 is2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone.

By the term ‘sulpho-compound-4’ is meant a compound represented by thefollowing formula L4

wherein R₉′ is a C₁-C₁₂ hydrocarbyl, and R₁₀′ is a C₁-C₁₂ hydrocarbyland R₁₁′ is a C₁-C₁₂ hydrocarbyl. An example of a sulpho-compound-4 ispentan-3-one O-tosyl oxime.

By the term ‘sulpho-compound-5’ is meant a compound represented by thefollowing formula L5

wherein R₁₂′ is a C₁-C₁₂ hydrocarbyl or a substituted hydrocarbyl, andR₁₃′ is a C₁-C₁₂ hydrocarbylene. An example of a sulpho-compound-5 is(E)-3,4-dihydronaphthalen-1(2H)-one O-((4-chlorophenyl)sulfonyl) oxime.

By the term ‘transition metal’ is meant a transition metal with atomicnumber of from and including 21 and up to and including 79. Examples oftransition metals include but are not limited to Sc, Ti, V, Cr, Mn, Fe,Co, Ni, Cu, Zn, Mo, and W.

By the term ‘transition metal compound’ is meant a monomeric compoundcomprising a transition metal in any valence. Examples of transitionmetal compounds include but are not limited to Cu⁺ salts, Cu²⁺ salts,Mn²⁺ salts, Mn³⁺ salts, Co²⁺ salts, Co³⁺ salts, Fe²⁺ salts and Fe³⁺salts.

The ‘stable radical’ is selected from the group consisting ofradicals-1, radicals-2, radicals-3, and radicals-4.

By the term ‘radical-1’ is meant an organic radical represented by thefollowing formula R-1

whereinD is selected from the group consisting of H, COOH, and OH; andRx₁ is a C₁-C₁₀ saturated hydrocarbyl, andRx₂ is a C₁-C₁₀ saturated hydrocarbyl, andRx₃ is a C₁-C₁₀ saturated hydrocarbyl, andRx₄ is a C₁-C₁₀ saturated hydrocarbyl, andExamples of a radical-1 include but are not limited to1-oxyl-2,2,6,6-tetramethylpiperidine,1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (a compound also referred toas TEMPOL), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine (a compoundalso referred to as 4-carboxy-TEMPO).

By the term ‘radical-2’ is meant an organic radical represented by thefollowing formula R-2

whereinRx₁ is a C₁-C₁₀ saturated hydrocarbyl, andRx₂ is a C₁-C₁₀ saturated hydrocarbyl, andRx₃ is a C₁-C₁₀ saturated hydrocarbyl, andRx₄ is a C₁-C₁₀ saturated hydrocarbyl, andA example of a radical-2 is 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one(a compound also referred to as TEMPON).

By the term ‘radical-3’ is meant an organic radical represented by thefollowing formula R-3

whereinD is selected from the group consisting of H, COOH, OH; andRx₁ is a C₁-C₁₀ saturated hydrocarbyl, andRx₂ is a C₁-C₁₀ saturated hydrocarbyl, andRx₃ is a C₁-C₁₀ saturated hydrocarbyl, andRx₄ is a C₁-C₁₀ saturated hydrocarbyl, andExamples of a radical-1 include but are not limited to1-oxyl-2,2,5,5-tetramethylpyrrolidine,1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also called3-carboxy-PROXYL).

By the term ‘radical-4’ is meant an organic radical represented by thefollowing formula R-4

whereinRx₁ is a C₁-C₁₀ saturated hydrocarbyl, andRx₂ is a C₁-C₁₀ saturated hydrocarbyl, andRx₃ is a C₁-C₁₀ saturated hydrocarbyl, andRx₄ is a C₁-C₁₀ saturated hydrocarbyl, andAn example of a radical-4 is galvinoxyl(2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy).

By the term ‘curing’ or ‘cure’ is meant the process of becoming ‘set’that is to form an irreversibly crosslinked network (the so-called‘cured form’), a material that can no longer flow, be melted ordissolved. Herein, the terms ‘curing’ ‘cure’ and ‘crosslinking’ are usedinterchangeably. The curing of a thermosetting powder coatingcomposition of the invention may take place with or without the use ofone or both of heat and radiation. If the curing of a thermosettingpowder coating composition takes place using only heat, then the curingis called ‘heat curing’. For clarity, the term heat curing does notinclude radiation induced curing. If the curing of a thermosettingpowder coating composition of the invention takes place using radiation,the curing is called ‘radiation curing’. Preferably, the curing of thethermosetting powder coating composition of the invention takes placevia heat curing. Optionally, a combination of heat and pressure can beused to cure a heat-curable thermosetting powder coating composition. Inthe context of the invention, the term ‘heat curing’ does not excludethe application of pressure along with heat in order to cure aheat-curable thermosetting powder coating composition, such as theheat-curable thermosetting powder coating composition of the invention.

By the term ‘heat-curable thermosetting powder coating compositioncomposition’ is meant a thermosetting powder coating composition thathas the ability to cure at atmospheric pressure and at a temperatureabove the room temperature (elevated temperature) and that heating atelevated temperature is necessary to induce and achieve the curing ofthe composition; radiation and pressure (above or below atmosphericpressure) are not excluded but are not necessary for the curing of saidcomposition.

By the term ‘radiation-curable thermosetting powder coating composition’is meant a thermosetting powder coating composition that has the abilityto cure at atmospheric pressure and upon radiation and that saidradiation is necessary to induce and achieve the curing of thecomposition; heating at elevated temperature and pressure (above orbelow atmospheric pressure) are not excluded but are not necessary forthe curing of said composition.

By the term ‘heat/radiation-curable thermosetting powder coatingcomposition’ is meant a thermosetting powder coating composition thatcan be one or both of a heat-curable and radiation-curable composition.

By the term ‘radiation’ is meant one or both of ultraviolet (UV)radiation and electron beam radiation.

By the term ‘extrudable’ referring to a thermosetting powder coatingcomposition is meant that once the components of said composition aremixed together, said mixture can be processed via an extruder.

By the term ‘very poor physical storage stability’ referring to athermosetting powder coating composition is meant that the thermosettingpowder coating composition upon storage at 23±1° C. for 7 weeks, has aphysical storage stability as this is assessed herein, of 1 (rating isbased on a scale from 1 to 10, with 1 being the worst and 10 the best).By the term ‘poor physical storage stability’ referring to athermosetting powder coating composition is meant that the thermosettingpowder coating composition upon storage at 23±1° C. for 7 weeks, has aphysical storage stability as this is assessed herein, of 2 (rating isbased on a scale from 1 to 10, with 1 being the worst and 10 the best).By the term ‘mediocre physical storage stability’ referring to athermosetting powder coating composition is meant that the thermosettingpowder coating composition upon storage at 23±1° C. for 7 weeks, has aphysical storage stability as this is assessed herein, of at least 3 andat most 4 (rating is based on a scale from 1 to 10, with 1 being theworst and 10 the best). By the term ‘good physical storage stability’referring to a thermosetting powder coating composition is meant thatthe thermosetting powder coating composition upon storage at 23±1° C.for 7 weeks, has a physical storage stability as this is assessedherein, of at least 5 and at most 6 (rating is based on a scale from 1to 10, with 1 being the worst and 10 the best). By the term ‘very goodphysical storage stability’ referring to a thermosetting powder coatingcomposition is meant that the thermosetting powder coating compositionupon storage at 23±1° C. for 7 weeks, has a physical storage stabilityas this is assessed herein, of at least 7 and at most 9 (rating is basedon a scale from 1 to 10, with 1 being the worst and 10 the best). By theterm ‘excellent physical storage stability’ referring to a thermosettingpowder coating composition is meant that the thermosetting powdercoating composition upon storage at 23±1° C. for 7 weeks, has a physicalstorage stability as this is assessed herein, of 10 (rating is based ona scale from 1 to 10, with 1 being the worst and 10 the best). Thephysical storage stability is abbreviated herein as PSS and it ismeasured according to the relevant method described in the Examples.

By the term ‘able to heat-cure fast at low temperature’ or equally ‘ableto heat-curing fast at low temperature’ or equally ‘able to fastheat-cure at low temperatures’ or equally ‘able to fast heat-curing atlow temperatures’ referring to a thermosetting powder coatingcomposition, is meant that said composition once applied on a MDFsubstrate and heat-cured at 95° C. for 3 minutes in an infra-red oven(without the application of UV-radiation), it affords a powder coatingthat can withstand at least 210 acetone double rubs. A thermosettingpowder coating composition which can heat-cure fast at low temperaturesis particularly suitable for coating heat-sensitive articles.

By the term ‘heat-cure at low temperature’ or equally ‘heat-curing atlow temperature’ is meant heat-cure at 95° C. for 3 minutes in aninfra-red oven (without the application of radiation).

By the term ‘heat-cure at very low temperature’ or equally ‘heat-curingat very low temperature’ is meant heat-cure at 85° C. for 30 minutes, inan infra-red oven (without the application of radiation).

By the term ‘very poor chemical resistance’ referring to a powdercoating, is meant that said powder coating can withstand at most 99acetone double rubs. By the term ‘poor chemical resistance’ referring toa powder coating is meant that said powder coating can withstand atleast 100 and at most 149 acetone double rubs. By the term ‘sufficientchemical resistance’ referring to a powder coating is meant that saidpowder coating can withstand at least 150 and at most 249 acetone doublerubs. By the term ‘good chemical resistance’ referring to a powdercoating is meant that said powder coating can withstand at least 250 andat most 449 acetone double rubs. By the term ‘very good chemicalresistance’ referring to a powder coating is meant that said powdercoating can withstand at least 450 and at most 499 acetone double rubs.By the term ‘excellent chemical resistance’ referring to a powdercoating is meant that said powder coating can withstand at least 500acetone double rubs. A powder coating that has at least good chemicalresistance is particularly suitable for coating heat-sensitive articles.

The acetone double rubs abbreviated herein as ADR are measured accordingto the relevant method described in the Examples.

By the term ‘sufficient smoothness’ referring to a powder coating, ismeant a smoothness as measured according to the relevant methoddescribed in the Examples, of ≥2.

By the term ‘poor smoothness’ referring to a powder coating, is meant asmoothness as measured according to the relevant method described in theExamples, of ≤1.

The ‘K’ represents the ratio of the total mol of the ethylenicunsaturations in B (herein Total Mol_(B)) divided to the total mol ofthe ethylenic unsaturations in A (herein Total Mol_(B)), and it iscalculated according to the following equation:

K=Total Mol_(A)/Total Mol_(B)

wherein

${{Total}\mspace{14mu} {Mol}_{A}} = {\sum\limits_{S = 1}^{N}\left( \frac{Ms}{WPUs} \right)}$and${{Total}\mspace{14mu} {Mol}_{B}} = {\sum\limits_{r = 1}^{n}\left( \frac{Mr}{WPUr} \right)}$

and whereinM_(s) is the amount of a curing agent which forms part of the componentB and WPU_(s) is the weight per unsaturation of said curing agent; andM_(r) is the amount of a UR which forms part of the component A andWPU_(r) is the weight per unsaturation of said UR. Each of the WPU_(s)and WPU_(r) is measured via ¹H-NMR spectroscopy as disclosed in thedescription for the measurement of WPU.

By ‘room temperature’ is meant a temperature of 23±1° C.

A ‘resin’ is herein understood to have the same meaning as it has to askilled person in thermosetting polymer chemistry, namely as a lowmolecular weight polymer comprising reactive moieties such as forexample ethylenic unsaturations, said resin is able to crosslink; saidreactive moieties via a chemical reaction preferably said chemicalreaction is induced by means of heat and/or radiation, ultimatelyconnect the polymer chains together through the formation of permanentcovalent (crosslink) bonds, resulting to the cured resin. The term ‘lowmolecular weight’ means a number average molecular weight (M_(n))ranging of from 200 up to and including 20000 Da. Preferably a resin hasa M_(n) of at least 200, more preferably of at least 205, even morepreferably of at least 210, most preferably of at least 215, especiallyof at least 220, more especially of at least 250, most especially of atleast 300, for example of at least 310, for example of at least 315, forexample of at least 350, for example of at least 400, for example of atleast 450, for example of at least 500, for example of at least 600, forexample of at least 700, for example of at least 800 for example atleast 1000, for example at least 1200, for example at least 1500, forexample at least 1800, for example at least 2000, for example at least2200 Da. Preferably, a resin has a M_(n) of at most 20000, morepreferably of at most 10000, even more preferably of at most 9000, mostpreferably of at most 8000, especially of at most 7000, more especiallyof at most 6000, most especially of at most 5000 Da. A resin isclassified as acid functional in case its hydroxyl value (OHV) is lowerthan its acid value (AV). A resin is classified as hydroxyl functionalin case its acid value is lower than its hydroxyl value.

The acid and hydroxyl values values are measured according to therelevant methods disclosed in the Examples.

By ‘urethane resin’ is meant a resin comprising urethane moieties . . .—NH—(C═O)—O— . . . .

By ‘composition’ is meant the combining and/or mixture of distinctchemical substances and/or components to form a whole.

By ‘vinyl functionalized urethane resin’ (VFUR) is meant a urethaneresin comprising vinyl groups . . . —CH═CH₂.

The term ‘vinyl groups’ is used herein interchangeably with the term‘vinyl unsaturations’.

The term ‘vinyl’ is used herein interchangeably with the term ‘ethenyl’.

By ‘vinyl ether functionalized urethane resin’ (VEFUR) is meant aurethane resin comprising vinyl ether groups (see chemical structure 1;

indicates a point of attachment of the vinyl ether group).

By ‘vinyl ester functionalized urethane resin’ (VESFUR) is meant aurethane resin comprising vinyl ester groups (see chemical structure 2;

indicates a point of attachment of the vinyl ester group).

By ‘vinyl (ether-ester) functionalized urethane resin’ (VEESFUR) ismeant a urethane resin comprising vinyl ether groups (see chemicalstructure 1) and vinyl ester groups (see chemical structure 2).

Vinyl ether functionalized urethane resins, vinyl ester functionalizedurethane resins and vinyl (ether-ester) functionalized urethane resinsas well as their preferred embodiments are each a vinyl functionalizedurethane resin.

By ‘vinyl urethane’ (VU) is meant a monomeric organic compoundcomprising urethane moieties . . . —NH—(C═O)—O— . . . and vinyl groups .. . —CH═CH₂.

By ‘vinyl ether urethane’ (VEU) is meant a monomeric organic compoundcomprising urethane moieties . . . —NH—(C═O)—O— . . . and vinyl ethergroups (see chemical structure 3;

indicates a point of attachment of the vinyl ether group).

By ‘vinyl ester urethane’ (VESU) is meant a monomeric organic compoundcomprising urethane moieties . . . —NH—(C═O)—O— . . . and vinyl estergroups (see chemical structure 4;

indicates a point of attachment of the vinyl ester group).

By ‘vinyl (ether-ester) urethane’ (VEESU) is meant a monomeric organiccompound comprising urethane moieties . . . —NH—(C═O)—O— . . . and vinylether groups (see chemical structure 3) and vinyl ester groups (seechemical structure 4).

Vinyl ether urethanes, vinyl ester urethanes and vinyl (ether-ester)urethanes as well as their preferred embodiments are each a vinylurethane.

By ‘powder’ is meant, a substantially dry solid substance at roomtemperature and at atmospheric pressure reduced to a state of fine,loose particles wherein the individual particles have preferably amaximum particle size of at most 200, more preferably of at most 180,even more preferably of at most 160, most preferably of at most 150,especially of at most 140, more especially of at most 130, mostespecially of at most 120, for example of at most 110, for example of atmost 100, for example of at most 90 μm at 23° C. and at atmosphericpressure; the individual particles have preferably a minimum particlesize of at least 5, more preferably of at least 10, even more preferablyof at least 15, most preferably of at least 20, especially of at least25, more especially of at least 30, most especially of at least 35, forexample of at least 40, for example of at least 45, for example of atleast 50, for example of at least 55 μm at 23° C. and at atmosphericpressure. A particle is defined as a small object that: a) has meanlinear dimensions as described herein after and b) behaves as a wholeunit in terms of its transport and properties. The particle sizedistribution (PSD) of a powder is a list of values or a mathematicalfunction that defines the relative amounts of particles present, sortedaccording to size. The terms ‘particle size’ and ‘particle sizedistribution’ will be used interchangeably in the context of theinvention when used in relation to a powder. The method used to measurethe particle size of the thermosetting powder coating compositions ofthe invention is sieve analysis. According to it, the powder isseparated on sieves of different sizes. Thus, the PSD is defined interms of discrete size ranges: e.g. ‘weight % of sample powder hasparticle size in the range of 75 microns to 90 microns’, when sieves ofthese sizes are used. Preferably, 70 weight % of the thermosettingpowder coating composition of the invention has a particle size in therange of 10 to 200 micron. The PSD can be determined for example by thefollowing method: a certain amount of thermosetting powder coatingcomposition, for example 100 g, is brought onto a Fritsch AnalysetteSpartan sieving apparatus equipped with a 200 micron sieve. The sampleis sieved for 15 minutes at a 2.5 mm amplitude. The fraction of thesample which remained on the sieve was weighed after sieving. Thefraction of the sample that went through the sieve (sieved fraction) iscollected and is placed on a 160 micron sieve and is sieved as mentionedherein above. Once the same measurements (weighing) are performed asmentioned herein above, the same procedure is repeated usingsequentially a 140, a 125, a 112, a 100, a 90, a 75, a 50, a 20 and a 10micron sieve; the last sieved fraction with a size smaller than 10micron is also weighed. Summing up the various weight fractions, thisshould yield the initial amount of sample, in this example 100 g. Thevarious weight fractions represent the PSD as a list of valuesrepresenting the relative amounts of particles present, sorted accordingto sieves used.

By ‘substantially dry’ is meant that the powder e.g. a thermosettingpowder composition, does not comprise any deliberately added water ormoisture but the powder may comprise moisture absorbed from theatmosphere in an amount of up to 30, preferably up to 20, morepreferably up to 10, even more preferably up to 5, most preferably up to3, especially up to 2, more especially up to 1% w/w based on the totalweight of the component.

By ‘thermosetting powder coating compositions’ or ‘powders’ is meant, amixture of components in the form of a powder and which compositionshave the ability to form an irreversible crosslinked network (theso-called ‘cured form’) upon curing, preferably via heat and/orradiation curing, more preferably via heat curing.

By ‘components of the thermosetting powder coating compositions of theinvention’ is meant constituent elements, their preferred embodimentsand combinations thereof, that constitute part of the thermosettingpowder coating composition of the invention; said components, theirpreferred embodiments and combinations thereof, should be construed inview of the whole disclosure; exemplary components include but are notlimited to component A, component B, component C, UR, VU,perdicarbonate-X, crystalline VU-c, crystalline VFUR-c, as each isdefined herein.

The terms amorphous and crystalline used to characterize a monomericcompound or a resin or a component of a composition are informal termsused in the art to indicate the predominant character of the relevantmonomeric compound or a resin or a component of a composition in respectto its degree of crystallinity but these terms are defined moreprecisely herein by melting enthalpy (ΔH_(m)) values. The term‘crystalline’ denotes both crystalline and semicrystalline

By ‘amorphous’ is meant that a monomeric compound, or a resin, or acomponent of a composition, for example a vinyl urethane or a vinylfunctionalized urethane resin or a UR has a melting enthalpy (ΔH_(m))<35J/g.

By ‘crystalline’ is meant that a monomeric compound, or a resin, or acomponent of a composition, for example a vinyl urethane or a vinylfunctionalized urethane resin or a UR has a melting enthalpy (ΔH_(m))≥35J/g.

By ‘crystalline VU-c’ is meant a crystalline vinyl urethane having amelting enthalpy ΔH_(m)≥35 J/g, and one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the crystalline VU-c are inthe region of from and including 30 up to and including 80° C.

By ‘crystalline VEU-c’ is meant a crystalline vinyl ether urethanehaving a melting enthalpy ΔH_(m)≥35 J/g, and one or more meltingtemperatures (T_(m)) wherein any and all of the T_(m) of the crystallineVEU-c are in the region of from and including 30 up to and including 80°C. A crystalline VEU-c is a species of a crystalline VU-c.

By ‘crystalline VESU-c’ is meant a crystalline vinyl ester urethanehaving a melting enthalpy ΔH_(m)≥35 J/g, and one or more meltingtemperatures (T_(m)) wherein any and all of the T_(m) of the crystallineVESU-c are in the region of from and including 30 up to and including80° C. A crystalline VESU-c is a species of a crystalline VU-c.

By ‘crystalline VEESU-c’ is meant a crystalline vinyl (ether-ester)urethane having a melting enthalpy ΔH_(m)≥35 J/g, and one or moremelting temperatures (T_(m)) wherein any and all of the T_(m) of thecrystalline VEESU-c are in the region of from and including 30 up to andincluding 80° C. A crystalline VEESU-c is a species of a crystallineVU-c.

By ‘crystalline VFUR-c’ is meant a crystalline vinyl functionalizedurethane resin having a melting enthalpy ΔH_(m)≥35 J/g, and one or moremelting temperatures (T_(m)) wherein any and all of the T_(m) of thecrystalline VFUR-c are in the region of from and including 30 up to andincluding 80° C.

By ‘crystalline VEFUR-c’ is meant a crystalline vinyl etherfunctionalized urethane resin having a melting enthalpy ΔH_(m)≥35 J/g,and one or more melting temperatures (T_(m)) wherein any and all of theT_(m) of the crystalline VEFUR-c are in the region of from and including30 up to and including 80° C. A crystalline VEFUR-c is a species of acrystalline VFUR-c.

By ‘crystalline VESFUR-c’ is meant a crystalline vinyl esterfunctionalized urethane resin having a melting enthalpy ΔH_(m)≥35 J/g,and one or more melting temperatures (T_(m)) wherein any and all of theT_(m) of the crystalline VESFUR-c are in the region of from andincluding 30 up to and including 80° C. A crystalline VESFUR-c is aspecies of a crystalline VFUR-c.

By ‘crystalline VEESFUR-c’ is meant a crystalline vinyl (ether-ester)functionalized urethane resin having a melting enthalpy ΔH_(m)≥35 J/g,and one or more melting temperatures (T_(m)) wherein any and all of theT_(m) of the crystalline VEESFUR-c are in the region of from andincluding 30 up to and including 80° C. A crystalline VEESFUR-c is aspecies of a crystalline VFUR-c.

By ‘T_(g)’ is meant the glass transition temperature. The T_(g) ismeasured using DSC (Differential Scanning Calorimetry) as describedherein.

By ‘T_(c)’ is meant the crystallization temperature; in case a monomeror a resin or a resin composition has multiple crystallization peaks,then the peak temperature of the crystallization peak with the largestcrystallization enthalpy (ΔH_(c)) is mentioned herein as T_(c). TheT_(c) is measured using DSC (Differential Scanning Calorimetry) asdescribed herein.

By ‘T_(m)’ is meant the melting temperature; in case a monomer or aresin or a resin composition or a compound has multiple meltings thenthe T_(m) of the melting with the largest melting enthalpy is mentionedherein as T_(m). The T_(m) is measured using DSC as described herein.

By ‘ΔH_(m)’ is meant the melting enthalpy. The (ΔH_(m)) is measuredusing DSC as described herein. In case a monomer or a resin or a resincomposition has more than one melting peaks then the melting enthalpy(ΔH_(m)) values mentioned herein, refer to the total of the meltingenthalpy (ΔH_(m)) said total obtained by summing up the ΔH_(m) values ofeach of the melting peaks.

By ‘ΔH_(C)’ is meant the crystallization enthalpy. The (ΔH_(c)) ismeasured using DSC as described herein. In case a monomer or a resin ora resin composition has more than one crystallization peaks then thecrystallization enthalpy (ΔH_(c)) values mentioned herein, refer to thetotal of the crystallization enthalpy (ΔH_(c)) said total obtained bysumming up the ΔH_(c) values of each of the crystallization peaks.

The glass transition temperature (T_(g)), melting temperature (T_(m)),crystallization temperature (T_(c)), melting enthalpy (ΔH_(m))crystallization enthalpy (ΔH_(c)), measurements are carried out viaDifferential Scanning Calorimetry (DSC) as described herein.

The acid value (AV) of a sample e.g. a resin or a curing agent (AV in mgKOH/g sample) is measured titrimetrically according to ISO 2114-2000.

The hydroxyl value (OHV) of a sample e.g. resin or a curing agent (OHVin mg KOH/g sample) is measured titrimetrically according to ISO4629-1978.

By ‘cured thermosetting powder coating composition’ is meant a form thatis obtained by partial or full curing of a thermosetting powder coatingcomposition; said curing may be effected via heat and/or radiation,preferably via heat; said form may have any shape or size and it can forexample be a film, coating; preferably the cured thermosetting powdercoating composition is a powder coating.

By ‘powder coating’ is meant the partially or fully cured form of athermosetting powder coating composition, the latter being preferablyheat- and/or radiation curable, said form being a coating. A powdercoating is obtained by curing of a thermosetting powder coatingcomposition.

By ‘article’ is meant an individual object or item or element of a classdesigned to serve a purpose or perform a special function and can standalone. A substrate is an example of an article.

By ‘di-acid’ as used herein means a dicarboxylic acid or anhydride ordiester or other derivatives of a dicarboxylic acid such as for examplesdicarboxylic acid salts; preferably ‘di-acid’ is a dicarboxylic acid oranhydride, more preferably ‘di-acid’ is a dicarboxylic acid.

By ‘ethylenic unsaturation’ as used herein means cis- ortrans-configured reactive carbon-carbon double bond unsaturation anddoes not include aromatic unsaturation, carbon-carbon triple bond,carbon-heteroatom unsaturation. Preferably, the ethylenic unsaturationcomprises at least a hydrogen which is covalently bonded to a carbon ofthe ethylenic unsaturation, more preferably the ethylenic unsaturationis a non-aromatic cis- or trans-configured carbon-carbon double bondunsaturation according to the following formula: . . . —CH═CH— . . . . Avinyl unsaturation is an example of an ethylenic unsaturation.

The term ‘di-acid ethylenic unsaturations’ as used herein meansethylenic unsaturations obtainable from any isomer of an unsaturateddi-acid and/or derivatives thereof, such as for example ethylenicunsaturations obtainable from a di-acid chosen from the group of2-butenedioic acid, 2-methyl-2-butenedioic acid, itaconic acid andmixtures thereof. Derivatives of any isomer of unsaturated di-acidsinclude esters, anhydrides, acid salts. Fumaric acid and maleic acid areisomers of 2-butenedioic acid, whereas citraconic acid and mesaconicacid are isomers of 2-methyl-2-butenedioic acid. For example ‘di-acidethylenic unsaturations’ may be obtainable from fumaric, maleic,itaconic, citraconic and/or mesaconic acids, derivatives thereof and/ormixtures thereof. Fumaric acid based unsaturation is an informal termused herein to denote unsaturation derived from fumaric acid, itsisomers e.g. maleic acid and/or derivatives thereof.

By ‘2-butenedioic acid ethylenic unsaturations’ as used herein meansdi-acid ethylenic unsaturations obtainable from any isomer of2-butenedioic acid and/or derivatives thereof. Fumaric acid and maleicacid are isomers of 2-butenedioic acid. Maleic acid is the cis-isomer of2-butenedioic acid, whereas fumaric acid is the trans-isomer of2-butenedioic acid. Derivatives of any isomer of 2-butenedioic acidinclude esters, anhydrides, acid salts.

By ‘unsaturated resin comprising ethylenic unsaturations’ or equallymentioned herein as ‘UR’, is meant an unsaturated resin having ethylenicunsaturations. For example an unsaturated polyester resin comprising2-butenedioic acid ethylenic unsaturations, an acrylated polyesterresin, a methacylated polyester resin, a (meth)acrylated polyesterresin, are each an unsaturated resin comprising ethylenic unsaturations.

By ‘unsaturated resin comprising di-acid ethylenic unsaturations’ ismeant an unsaturated resin having di-acid ethylenic unsaturations; saidresin is a sub-class of an unsaturated resin comprising ethylenicunsaturations. For example an unsaturated polyester resin comprisingdi-acid ethylenic unsaturations is an unsaturated resin comprisingdi-acid ethylenic unsaturations.

By ‘unsaturated resin comprising 2-butenedioic acid ethylenicunsaturations’ is meant an unsaturated resin having 2-butenedioic acidethylenic unsaturations; said resin is a sub-class of an unsaturatedresin comprising di-acid ethylenic unsaturations and thus a furthersub-class of an unsaturated resin comprising ethylenic unsaturations.For example an unsaturated polyester resin having 2-butenedioic acidethylenic unsaturations is an unsaturated resin comprising 2-butenedioicacid ethylenic unsaturations.

By ‘unsaturated polyester resin comprising ethylenic unsaturations’ orequally ‘unsaturated polyester resin having ethylenic unsaturations’ ismeant, an unsaturated polyester resin having ethylenic unsaturations.

By ‘unsaturated polyester resin comprising di-acid ethylenicunsaturations’ or equally ‘unsaturated polyester resin having di-acidethylenic unsaturations’ is meant, an unsaturated polyester resin havingdi-acid ethylenic unsaturations; said polyester resin is a sub-class ofan unsaturated polyester resin comprising ethylenic unsaturations

By ‘unsaturated polyester resin comprising 2-butenedioic acid ethylenicunsaturations’ or equally ‘unsaturated polyester resin having2-butenedioic acid ethylenic unsaturations’ is meant, an unsaturatedpolyester resin having 2-butenedioic acid ethylenic unsaturations. The‘unsaturated polyester resin comprising 2-butenedioic acid ethylenicunsaturations’ may for example be prepared from any isomer of2-butenedioic acid and/or derivatives thereof. Fumaric acid and maleicacid are isomers of 2-butenedioic acid. Maleic acid is the cis-isomer of2-butenedioic acid, whereas fumaric acid is the trans-isomer of2-butenedioic acid. Derivatives of any isomer of 2-butenedioic acidinclude esters, anhydrides, acid salts. Maleic acid and maleic acidanhydride partly isomerize to fumaric acid when used in the synthesis ofa polyester resin comprising 2-butenedioic acid ethylenic unsaturations.

The ‘curing agent’ is selected from the group consisting of vinylurethanes, vinyl functionalized urethane resins and mixtures thereof.

By ‘curing agent A’ is meant a curing agent selected from the groupconsisting of i), ii) and iii):

-   -   i) one or more crystalline VU-c each of which is a crystalline        vinyl urethane having a melting enthalpy ΔH_(m)≥35 J/g and one        or more melting temperatures (T_(m)) wherein any and all of the        T_(m) of the one or more crystalline VU-c are in the region of        from and including 30 up to and including 80° C., and    -   ii) one or more crystalline VFUR-c each of which is a        crystalline vinyl functionalized urethane resin having a melting        enthalpy ΔH_(m)≥35 J/g and one or more melting temperatures        (T_(m)) wherein any and all of the T_(m) of the one or more        crystalline VFUR-c are in the region of from and including 30 up        to and including 80° C., and    -   iii) mixtures of crystalline VU-c and crystalline VFUR-c,        wherein the ΔH_(m) and T_(m) is each measured via Differential        Scanning Calorimetry (DSC) according to the description.

By ‘thermal radical initiator’ is meant any monomeric organic ormonomeric inorganic compound that upon heating and without theapplication of UV-radiation is able to generate free radicals, forexample via decomposition and initiate radical crosslinking in thethermosetting powder coating composition of the invention; preferablythe thermal radical initiator is able to generate free radicals withoutthe application of UV-radiation upon being heated at temperatures of upto 230° C., more preferably the thermal radical initiator is able togenerate free radicals without the application of UV-radiation uponbeing heated at temperatures of from and including 20 up to andincluding 170° C. Preferably, the thermal radical initiator is anymonomeric organic compound that upon heating and without the applicationof UV-radiation is able to generate free radicals, for example viadecomposition and initiate radical crosslinking in the thermosettingpowder coating composition of the invention; preferably the thermalradical initiator is able to generate free radicals without theapplication of UV-radiation upon being heated at temperatures of up to230° C., more preferably upon being heated at temperatures of from andincluding 20 up to and including 170° C. Preferably the thermal radicalinitiator is selected from the group consisting of organic peroxides,azo compounds, and mixtures thereof, more preferably the thermal radicalinitiator is selected from the group consisting of organic peroxides.Exemplary organic peroxides include but are not limited tohydroperoxides, ketone peroxides, peroxyketals, perethers, peroxyesters(also known as peresters), monopercarbonates, peroxydicarbonates,peranhydrides. Exemplary azo compounds include but are not limited toazo isobutyronitrile (AIBN), 1,1′-azobis(cyclohexanenitrile),1,1′-azobis(2,4,4-trimethylpentane).

By the term ‘photoinitiator’ is meant any monomeric organic or monomericinorganic compound that is capable to generate free radicals uponexposure to UV-radiation without the application of heat, and isselected from the group of compounds consisting of i), ii), iii) iv), v)and vi):

i) acyl phosphines such as bis-acyl phosphine oxides such as2,4,6,-trimethylbenzoyl diphenylphosphine oxide, and

ii) a-hydroxy ketones, and

iii) α-cleavage free radical photoinitiators including benzoin and itsderivatives such as benzoin ethers such as isobutyl benzoin ether, andbenzyl ketals such as benzyl dimethyl ketal,2-hydroxy-2-methyl-1-phenylpropan-1-one and4-(2-hydroxyethoxy)phenyl-2-hydroxy-2-propyl ketone, and

iv) aryl ketones such as 1-hydroxycyclohexyl phenyl ketone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one,2,2-dimethoxy-2-phenylaceto-phenone, mixture of benzophenone and1-hydroxycyclohexyl phenyl ketone, and2-methyl-1-(4-(methylthiophenyl)-2-(4-morpholinyl))-1-propanone, and

v) hydrogen abstraction free radical type photoinitiators such asMichler's ketone (4-4′-bisdimethylamino benzophenone), Michler's ethylketone (4-4′-bisdiethylamino benzophenone ethyl ketone), benzophenone,thioxanthone, anthroquinone, d,l-camphorquinone, ethyld,l-ccamphorquinone, ketocoumarin, anthracene and derivatives of each ofthem, and

vi) any mixture of i), ii), iii), iv) and v).

The ‘ethoxylated hydroxybutyl vinyl ether-X’ is selected from the groupof compounds represented by the following formula HBVE(EO) and mixturesthereof

wherein n is an integer selected from the group consisting of 1, 2, 3,4, and 5. Examples of compounds of formula HBVE(EO) include3,6,9,14-tetraoxahexadec-15-en-1-ol (wherein n=1), and3,6,9,12,17-pentaoxanonadec-18-en-1-ol (wherein n=3), and3,6,9,12,15,18,23-heptaoxapentacos-24-en-1-ol (wherein n=5).

Certain moieties, species, groups, repeat units, compounds, oligomers,polymers, materials, mixtures, compositions and/or formulations whichcomprise and/or are used in some or all of the invention as describedherein may exist as one or more different forms such as any of those inthe following non exhaustive list: stereoisomers (such as enantiomers(e.g. E and/or Z forms), diastereoisomers and/or geometric isomers);tautomers (e.g. keto and/or enol forms). The invention comprises and/oruses all such forms which are effective as defined herein.

By ‘M_(n)’ is meant the number average molecular weight and it ismeasured as disclosed herein.

By ‘mg/Kg A and B’ is meant mg (=10⁻³ g) per 1 Kg of the total ofcomponents A and B together. For example if in a TPCC of the inventionthe total amount of component E is 900 mg and the amounts of componentsA and B in the TPCC of the invention are 2 Kg and 1 Kg respectively,then the total amount of component E in said TPCC is 300 mg/Kg A and B.

By ‘mmol/Kg A and B’ is meant mmol (=10⁻³ mol) per 1 Kg of the total ofcomponents A and B together. For example if in a TPCC of the inventionthe total amount of component C is 2000 mmol and the amounts ofcomponents A and B in the TPCC of the invention are 5 Kg and 5 Kgrespectively, then the total amount of component C in said TPCC is 200mmol/Kg A and B.

By ‘pph’ is meant weight parts per one hundred weight parts.

By ‘pph of A and B’ (or equally ‘pph A and B’) is meant weight parts perone hundred weight parts of the total of components A and B together.For example if in a TPCC of the invention the total amount of componentB is 20 Kg and the amount of component A in the TPCC of the invention is80 Kg, then component B is present in an amount of 20 pph A and B; thus,in this particular example since B is present in an amount of 20 weightparts, at the same time A is present in an amount of 80 weight parts.

By ‘WPU’ is meant the measured weight per ethylenic unsaturation, unlessotherwise stated; the WPU is measured using ¹H-NMR spectroscopy asdescribed in the Examples [see Examples, ¹H-NMR method for themeasurement of the WPU (¹H-NMR method WPU)].

By ‘viscosity’ (q) is meant the melt viscosity (in Pa·s) at 160° C.Viscosity measurements were carried out at 160° C., on a Brookfield CAP2000+H Viscometer. The applied shear-rate was 70 s⁻¹ and a 19.05 mmspindle (cone spindle CAP-S-05 (19.05 mm, 1.8°) was used.

By ‘decomposition temperature of the component C’, is meant thetemperature (rounded up to the nearest integer) ±1° C., wherein thecomponent C has a half-life time of 6 minutes, said temperature beenmeasured via Differential Scanning Calorimetry-Thermal ActivityMonitoring (DSC-TAM) of a 0.1M solution of the component C inmonochorobenzene. The half-life time of the component C at a giventemperature, is the time required to reduce the initial amount of thecomponent C by 50%, at said given temperature.

By ‘(N)IR lamp’ denotes herein both a near-IR lamp and an IR lamp.

By the term ‘lower than’ is meant that the relevant maximum boundaryvalue is not included in the range.

By the term ‘higher than’ is meant that the relevant minimum boundaryvalue is not included in the range.

For all upper and lower boundaries of any parameters given herein, theboundary value is included in each range for each parameter. Allcombinations of minimum and maximum values of the parameters describedherein may be used to define the parameter ranges for variousembodiments and preferences of the invention.

In the context of the invention unless stated to the contrary, thedisclosure of alternative values for the upper or lower limit of thepermitted range of a parameter, coupled with an indication that one ofsaid values is more highly preferred than the other, is to be construedas an implied statement that each intermediate value of said parameter,lying in between the more preferred and the less preferred of saidalternatives, is itself preferred to said less preferred value and alsoto each value lying between said less preferred value and saidintermediate value.

The term ‘comprising’ as used herein means that the list thatimmediately follows is non-exhaustive and may or may not include anyother additional suitable items, for example one or more furtherfeature(s), component(s) and/or substituent(s) as appropriate. The term‘comprising’ will be used interchangeably with the term ‘containing’.“Substantially comprising” as used herein means a component or list ofcomponent(s) is present in a given material in an amount greater than orequal to about 90% w/w, preferably greater than or equal to 95% w/w,more preferably greater than or equal to 98% w/w, even more preferablygreater than or equal to 99% w/w of the total amount of the givenmaterial. The term ‘consisting of’ as used herein mean that the listthat follows is exhaustive and does not include additional items.

It will be understood that the total sum of any quantities expressedherein as percentages cannot (allowing for rounding errors) exceed 100%.For example the sum of all components of which the composition of theinvention (or part(s) thereof) comprises may, when expressed as a weight(or other) percentage of the composition (or the same part(s) thereof),total 100% allowing for rounding errors. However where a list ofcomponents is non-exhaustive the sum of the percentage for each of suchcomponents may be less than 100% to allow a certain percentage foradditional amount(s) of any additional component(s) that may not beexplicitly described herein. Unless the context clearly indicatesotherwise, as used herein plural forms of the terms herein (for examplecomposition, compound, component, resin, minute) are to be construed asincluding the singular form and vice versa.

1. The Thermosetting Powder Coating Composition of the Invention

Any and all of the thermosetting powder coating compositions disclosedin this section 1 (including any and all sub-sections) are collectivelyreferred to—in the whole of the application—as the ‘thermosetting powdercoating composition of the invention’. By ‘thermosetting powder coatingcomposition of the invention’ (or equally ‘TPCC of the invention’) ismeant a thermosetting powder coating composition of the inventionaccording to the invention. Unless otherwise explicitly stated, the term‘thermosetting powder coating composition of the invention’ as usedherein includes any and all of its components, preferments, combinationsof its features and ranges as well as combinations of any and all of itscomponents, preferments with any and all of the combinations of itscomponents, preferments, features and ranges. Thus, any and all of thethermosetting powder coating compositions disclosed in this section 1(including any and all sub-sections) includes any and all of itscomponents, preferments, combinations of its features and ranges as wellas combinations of any and all of its components, preferments with anyand all of the combinations of its components, preferments, features andranges, are collectively referred to—in the whole of the application—asthe thermosetting powder coating composition of the invention. Anyreference in this application as to the ‘thermosetting powder coatingcompositions as disclosed herein’ refers to the thermosetting powdercoating composition of the invention.

Broadly in accordance with the invention, there is provided athermosetting powder coating composition as described in the claims andas disclosed herein.

More particularly broadly in accordance with the invention there isprovided a thermosetting powder coating composition according to any oneof P1a and P1b.

Preferably, the thermosetting powder coating composition comprises thefollowing components A to C:

-   -   A: one or more unsaturated resins comprising ethylenic        unsaturations (UR), each of which is an unsaturated polymer        having ai) and aii):        -   ai) a number average molecular weight (M_(n)) of at least            200 and at most 20000 Da, and        -   aii) ethylenic unsaturations which are cis- or            trans-configured reactive carbon-carbon double bond            unsaturations and do not include aromatic unsaturations,            carbon-carbon triple bonds, carbon-heteroatom unsaturations;            and    -   wherein the UR is selected from the group consisting of        polyester resins, acrylic resins, polyurethanes, epoxy resins,        polyamides, polyesteramides, polycarbonates, polyureas and        mixtures thereof, and    -   B: one or more curing agents selected from the group consisting        of vinyl urethanes, vinyl functionalized urethane resins and        mixtures thereof, wherein at least one curing agent is curing        agent A which is selected from the group consisting of i), ii)        and iii):        -   i) one or more crystalline VU-c each of which is a            crystalline vinyl urethane having a melting enthalpy ΔH_(m)            35 J/g, and one or more melting temperatures (T_(m)) wherein            any and all of the T_(m) of the one or more crystalline VU-c            are in the region of from and including 30 up to and            including 80° C., and        -   ii) one or more crystalline VFUR-c each of which is a            crystalline vinyl functionalized urethane resin having a            melting enthalpy ΔH_(m)≥35 J/g, and one or more melting            temperatures (T_(m)) wherein any and all of the T_(m) of the            one or more crystalline VFUR-c are in the region of from and            including 30 up to and including 80° C., and        -   iii) mixtures of crystalline VU-c and crystalline VFUR-c,            wherein the ΔH_(m) and T_(m) is each measured via            Differential Scanning Calorimetry (DSC) according to the            description and the M_(n) is measured via Gel Permeation            Chromatography (GPC) according to the description, and    -   C: one or more thermal radical initiators, wherein at least one        thermal radical initiator is peroxydicarbonate-X which is        present in an amount of at least 26 and at most 500 mmol/Kg A        and B, and wherein the peroxydicarbonate-X is selected from the        group consisting of peroxydicarbonates represented by the        following formula X, and mixtures thereof,

-   -   wherein R₁ is C₉-C₂₂ saturated hydrocarbyl, and R₂ is C₉-C₂₂        saturated hydrocarbyl.

Preferably the thermosetting powder coating composition of the inventionhas a glass transition temperature (T_(g)) of at least 20 and at most80, more preferably at least 25 and at most 70, even more preferably atleast 25 and at most 60, most preferably at least 25 and at most 55,especially at least 25 and at most 50, more especially at least 30 andmost 80, even more especially at least 30 and at most 70, mostespecially at least 30 and at most 60, for example at least 30 and atmost 55, for example at least 30 and at most 50° C.

The various components of the thermosetting powder coating compositionsof the invention, and their preferments, including any and all theirfeatures, ranges are disclosed in the sub-sections of section 1.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1 including sub-sections 1.2 to 1.7 and their sub-sections, canbe combined with each other and with any other feature, element,component, embodiment, aspect, range and especially any preferredfeature, preferred element, preferred embodiment, preferred aspect,preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

1.1 the Component A of the TPCC of the Invention: Unsaturated ResinsComprising Ethylenic Unsaturations (UR)

The TPCC of the invention comprises component A wherein component Arepresents one or more unsaturated resins comprising ethylenicunsaturations (UR) selected from the group consisting of polyesterresins, acrylic resins, polyurethanes, epoxy resins, polyamides,polyesteramides, polycarbonates, polyureas and mixtures thereof.

More specifically, the TPCC of the invention comprises component Awherein component A represents one or more unsaturated resins comprisingethylenic unsaturations (UR) selected from the group consisting ofpolyester resins, acrylic resins, polyurethanes, epoxy resins,polyamides, polyesteramides, polycarbonates, polyureas and mixturesthereof, and wherein each of which has ai) and aii):

-   -   ai) a number average molecular weight (M_(n)) of at least 200        and at most 20000 Da, preferably of at least 1000 and at most        10000 Da, and    -   aii) ethylenic unsaturations which are cis- or trans-configured        reactive carbon-carbon double bond unsaturations and do not        include aromatic unsaturations, carbon-carbon triple bonds,        carbon-heteroatom unsaturations.

Preferably, in the TPCC of the invention the component A is present inan amount of at least 10 and at most 96, more preferably in an amount ofat least 15 and at most 90, even more preferably in an amount of atleast 40 and at most 85, most preferably in an amount of at least 45 andat most 84 pph of A and B.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.1 can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

Preferably the UR is selected from the group consisting of polyesterresins, polyurethanes, polyamides, polyesteramides, polyureas; mostpreferably the UR is selected from the group consisting of unsaturatedpolyester resins, acrylic resins (polyacrylates), unsaturatedpolyurethanes, unsaturated epoxy resins, unsaturated polyamides,unsaturated polyesteramides, unsaturated polycarbonates, unsaturatedpolyureas and mixtures thereof; especially the UR is selected from thegroup consisting of unsaturated polyester resins, unsaturatedpolyurethanes, unsaturated polyamides, unsaturated polyesteramides,unsaturated polyureas and mixtures thereof. For example the UR is apolyester resin; most preferably the UR is an unsaturated polyesterresin; most preferably the UR is an unsaturated polyester resincomprising ethylenic unsaturations such as acrylated polyester resins,unsaturated polyester resins comprising di-acid ethylenic unsaturations,unsaturated polyester resins comprising 2-butenedioic acid ethylenicunsaturations; especially the UR is an unsaturated polyester resincomprising di-acid ethylenic unsaturations; more especially the UR is anunsaturated polyester resin comprising 2-butenedioic acid ethylenicunsaturations.

The UR may be a polyacrylate, also known as acrylic resin. Generally, anacrylic resin is based on alkyl esters of acrylic acid or methacrylicacid, optionally in combination with styrene. These alkyl esters ofacrylic or methacrylic acid may be replaced by hydroxyl or glycidylfunctional acrylic or methacrylic acids. Exemplary alkyl esters ofacrylic or methacrylic acids include but are not limited to ethylmethacrylate, ethyl acrylate, isopropyl methacrylate, isopropylacrylate, n-butyl methacrylate, n-butyl acrylate, n-propyl methacrylate,n-propyl acrylate, isobutyl methacrylate, isobutyl acrylate, ethylhexylacrylate, cyclohexyl methacrylate, cyclohexyl acrylate and mixturesthereof. To obtain an acrylic resin having a hydroxyl functionality, theacrylic resin contains a hydroxyl functional (meth)acrylic acid [by theterm ‘(meth)acrylic’ is meant ‘methacrylic or acrylic’], preferably incombination with alkyl esters of (meth)acrylic acid. Examples ofhydroxyl functional (meth)acrylic acid esters include hydroxyethyl(meth)acrylate, and hydroxypropyl (meth)acrylate etc. To obtain anacrylic resin having a glycidyl functionality, the acrylic resincontains a glycidyl functional (meth)acrylic acid esters, preferably incombination with alkyl esters of (meth)acrylic acid. Examples ofglycidyl functional (meth)acrylic acid esters include glycidylmethacrylate, etc. It is also possible to synthesize acrylic resins withboth hydroxyl and glycidyl functionality. The introduction of ethylenicunsaturations to an acrylic resin may be carried out by reacting thehydroxyl and/or glycidyl moieties on the acrylic resin with anunsaturated organic acid such as acrylic acid, methacrylic acid,2-butenedioic acid.

The UR may be a polyurethane. In the context of the invention the term‘polyurethane’ does not include vinyl functionalized urethane resins(VFUR). In other words the UR may be a polyurethane other than a VFUR.Polyurethanes can for example be prepared using customary, generallyknown polyaddition reaction of a (poly)isocyanate with a (poly)alcoholin the presence of, if needed a catalyst and other additives. Forexample, if needed, customary catalysts such as, for example tertiaryamines or organometallic compounds, such as for example monobutyltin,tris(2-ethylhexanoate), tetrabutyl titanate or dibutyl tin dilaurate canbe used. Examples of amounts of these catalysts used are usually around0.01 wt % based on the total weight of the resin. Examples of the(poly)alcohols that may be used in the preparation of polyurethanes arethe same as those that can be used in the preparation of a polyesterresin. Examples of isocyanates that may be used in the preparation ofpolyurethanes include but are not limited to those mentioned herein forthe preparation of the VFUR. The introduction of ethylenic unsaturationsto a polyurethane resin may be carried out by reacting the isocyanatemoieties on the polyurethane resin with an unsaturated hydroxylfunctional ester such as hydroxyl propyl methacrylate or hydroxyl ethylacrylate or hydroxyl ethyl methacrylate; alternatively the introductionof ethylenic unsaturations to a polyurethane resin may be carried out byreacting the hydroxyl moieties on the polyurethane with an unsaturatedorganic acid such as acrylic acid, methacrylic acid, 2-butenedioic acid.

The UR may be an epoxy resin. Epoxy resins may for example be preparedfrom phenolic compounds in combination with epichlorohydrins resultingin epoxy resins like for example a bisphenol A diglycidyl ether such asis commercially available as Epikote™ 1001 or a Novolac epoxide. Theintroduction of ethylenic unsaturations to an epoxy resin may be carriedout by reacting the epoxy moieities on the epoxy resin with anunsaturated organic acid such as acrylic acid, methacrylic acid,2-butenedioic acid.

The UR may be a polyamide. Polyamides can for example be prepared by apolycondensation reaction of a diamine and a dicarboxylic acid. Thedicarboxylic acids may be branched, non-linear or linear. Exemplarydicarboxylic acids include but are not limited to phthalic acid,isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid,naphthalene-2,6-dicarboxylic acid, cyclohexanediacetic acid,diphenyl-4,4′-dicarboxylic acid, phenylenedi (oxyacetic acid), sebacicacid, succinic acid, adipic acid, glutaric acid and/or azelaic acid.Exemplary diamines include but are not limited to isophorondiamine,1,2-ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine,1,12-dodecylenediamine, 1,4 cyclohexanebismethylamine, piperazine,p-xylylenediamine and/or m-xylylenediamine. The polyamide may also bebranched using branching agents. Exemplary branching agents include butare not limited to amines for example di-alkylene-triamines, such as forexample di-ethylene-triamine or di-hexamethylene-triamine;di-alkylene-tetramines or di-alkylene-pentamines; acids, for example1,3,5-benzene tricarboxylic acid, trimellitic anhydride or pyromeliticanhydride; and poly-functional amino acids, such as for example asparticacid or glutamic acid. The introduction of ethylenic unsaturations maybe carried out by reacting the carboxyl moieities on a polyamide resinwith an unsaturated organic alcohol, such as hydroxyethylacrylate,hydroxyethylmethacrylate. The UR may be a polyesteramide.Polyesteramides are resins comprising both ester bonds (as in apolyester) and amide bonds (as in a polyamide) and may for example beprepared from mono-, di-, tri- or polyfunctional monomers, such asmonomers with carboxylic acid functionality, monomers with hydroxylfunctionality, monomers with amine functionality and/or monomers havinga combination of any of these functionalities. The introduction ofethylenic unsaturations may be carried out by reacting the carboxylmoieities on a polyesteramide resin with an unsaturated organic alcohol,such as hydroxyethyl(meth)acrylate. The UR may be a polycarbonate. Theintroduction of ethylenic unsaturations to a polycarbonate may becarried out by reacting the hydroxyl moieities on the polycarbonate withan unsaturated organic acid such as acrylic acid, methacrylic acid,2-butenedioic acid.

The UR may be a polyurea. Polyureas can for example be prepared usingcustomary, generally known polyaddition reactions of a (poly)isocyanatewith a (poly)amine in the presence of, if needed a catalyst and otheradditives similar to what is described above for polyurethanes. Suitable(poly)amines for the preparation of polyureas include those as areexemplified above for the polyamides. Suitable (poly)isocyanates for thepreparation of polyureas include those as are exemplified above for thepolyurethanes. The introduction of ethylenic unsaturations to a polyureamay be carried out by reacting the amine and/or isocyanate moieties inthe polyurea with an unsaturated organic acid such as acrylic acid,methacrylic acid, 2-butenedioic acid.

The UR may be an unsaturated polyester resin such as an acrylatedpolyester resin or a polyster comprising ethylenic unsaturations in itsbackbone; preferably the UR is an unsaturated polyester resin comprisingethylenic unsaturations such as acrylated polyester resins, unsaturatedpolyester resins comprising di-acid ethylenic unsaturations, unsaturatedpolyester resins comprising 2-butenedioic acid ethylenic unsaturations;especially the UR is an unsaturated polyester resin comprising di-acidethylenic unsaturations; more especially the UR is an unsaturatedpolyester resin comprising 2-butenedioic acid ethylenic unsaturations.The unsaturated polyester resins comprising ethylenic unsaturations maybe amorphous or crystalline. The unsaturated polyester resin comprisingdi-acid ethylenic unsaturations may be amorphous or crystalline. Theunsaturated polyester resins comprising 2-butenedioic acid ethylenicunsaturations may be amorphous or crystalline.

Polyesters (or commonly known in the art as polyester resins) aregenerally polycondensation products of polyols and polycarboxylic acids.According to the invention a polyester resin is preferably thepolycondensation product of polyols and polycarboxylic acids, morepreferably a polyester resin is the polycondensation product ofdicarboxylic acids, di-alcohols (diols) and/or trifunctional alcoholsand/or trifunctional carboxylic acids.

Examples of polycarboxylic acids, especially dicarboxylic acids whichmay be used in the preparation of a polyester resininclude isophthalicacid, terephthalic acid, hexahydroterephthalic acid,2,6-naphthalenedicarboxylic acid and 4,4′-oxybisbenzoic acid,3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalicacid, hexahydroterephthalic acid,hexachloroendomethylenetetrahydrophthalic acid,endomethylenetetrahydrophthalic acid, phthalic acid, azelaic acid,sebacic acid, decanedicarboxylic acid, adipic acid, succinic acid andtrimellitic acid. These illustrative polycarboxylic acids can be used intheir acid form or where available, in the form of their anhydrides,acyl chlorides or lower alkyl esters. Mixtures of polycarboxylic acidscan also be used. In addition hydroxycarboxylic acids and lactones canbe used. Examples include hydroxypivalic acid and ε-caprolactone.

Polyols, in particular diols, can be reacted with the carboxylic acidsor their analogues as described above to prepare the polyester resin.Examples of polyalcohols include aliphatic diols, for example, ethyleneglycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol,butane-1,4-diol, butane-1,3-diol, 2,2-dimethylpropane-1,3-diol(neopentyl glycol), hexane-2,5-diol, hexane-1,6-diol,2,2-bis-(4-hydroxycyclohexyl)-propane (hydrogenated bisphenol-A),1,4-dimethylolcyclohexane, diethylene glycol, dipropylene glycol and2,2-bis[4-(2-hydroxyethoxy)-phenyl]propane, the hydroxypivalic ester ofneopentylglycol and 4,8-bis-(hydroxymethyl)tricyclo[5,2,1,0]decane(=tricyclodecane dimethylol) and 2,3-butenediol.

Monofunctional carboxylic acids, for example para-tert-butyl benzoicacid, benzoic acid, methyl benzoic acid, cinnamic acid, crotonic acidmay be used to block the polymer chain.

Trifunctional or more functional alcohols or carboxylic acids can beused to obtain branched polyester resins. Examples of suitabletrifunctional or more functional alcohols or carboxylic acids includebut not limited to glycerol, hexanetriol, trimethylol ethane,trimethylol propane, pentaerythritol and sorbitol, trimellitic acid,trimellitic acid anhydride, pyromellitic acid dimethylolpropionic acid(DMPA). To obtain branched polyester resins trifunctional monomers suchas trimethylolpropane may be used.

The polyester resins can be prepared via customary, generally knownpolymerization methods by conventional esterification and/ortransesterification or by esterification and/or transesterification viathe use of an enzyme. For example, if needed, customary esterificationcatalysts such as, for example, butylchlorotindihydroxide, dibutyltinoxide, tetrabutyl titanate or butyl stannoic acid can be used. Examplesof amounts of these esterification catalysts used are usually around 0.1wt % based on the total weight of the polyester resin.

The conditions for preparing a polyester resin and the COOH/OH ratio canbe chosen such that end products are obtained which have an acid valueor hydroxyl value which is within the intended range of values.

The polyester resins used in the thermosetting powder coatingcompositions of the invention are unsaturated polyester resinscomprising ethylenic unsaturations, preferably comprising di-acidethylenic unsaturations, more preferably comprising 2-butenedioic acidethylenic unsaturations; said ethylenic unsaturations may be present inthe backbone of the polyester resin and/or pendant to the backbone ofthe polyester resin and/or at the terminus of the polyester resin.Preferably, said ethylenic unsaturations are in the backbone of thepolyester resin and/or pendant to the backbone of the polyester resin,more preferably said ethylenic unsaturations are in the backbone of thepolyester resin; said ethylenic unsaturations may be built into thepolyester resin backbone, for instance by reacting a hydroxyl functionalmonomer (such as the polyalcohols mentioned before) with an unsaturateddi-acid monomer as mentioned above. It is also possible to connect thedi-acid ethylenic unsaturation to the terminus (or termini) of thepolyester resin, for example by reacting a hydroxyl functional terminalgroup of the polyester resin with an unsaturated di-acid monomer or itscorresponding anhydride as mentioned above.

Acrylated polyester resins are unsaturated polyester resins comprisingethylenic unsaturations said ethylenic unsaturations being derived frommethacrylic acid, acrylic acid, ethylenically unsaturated glycidylfunctional monomer, such as for example glycidyl methacrylate orglycidyl acrylate; in the acrylated polyester resins said ethylenicunsaturations are typically at the terminus (or termini) of theunsaturated polyester resin. Acrylated polyester resins may be preparedby reacting for example a hydroxyl or an epoxy or an amine functional(preferably also terminal) group of a polyester resin with methacrylicacid, acrylic acid, ethylenically unsaturated glycidyl functionalmonomer, such as for example glycidyl methacrylate or glycidyl acrylate.Alternatively, an acrylated polyester resin may be prepared by reactinga carboxyl functional (preferably also terminal) group of a polyesterresin with an ethylenically unsaturated glycidyl functional monomer,such as for example glycidyl methacrylate or glycidyl acrylate.

Preferably polyester resins comprising di-acid ethylenic unsaturationshave di-acids chosen from the group consisting of any isomer of2-butenedioic acid, 2-methyl-2-butenedioic acid, itaconic acid andmixtures thereof. Derivatives of any isomer of unsaturated di-acidsinclude esters, anhydrides, acid salts. Fumaric acid and maleic acid areisomers of 2-butenedioic acid, whereas citraconic acid and mesaconicacid are isomers of 2-methyl-2-butenedioic acid. For example ‘di-acidethylenic unsaturations’ may be obtainable from fumaric, maleic,itaconic, citraconic and/or mesaconic acids, derivatives thereof and/ormixtures thereof. Fumaric acid based unsaturation is an informal termused herein to denote unsaturation derived from fumaric acid, itsisomers e.g. maleic acid and/or derivatives thereof. More preferably thedi-acids are chosen from the group consisting of any isomer of2-butenedioc acid, itaconic acid and mixtures thereof, even more thedi-acids are chosen from the group consisting of any isomer of2-butenedioc acid. Besides 2-butenedioic acid ethylenic unsaturations,the unsaturated polyester resin may of course also have other di-acidethylenic unsaturations.

Preferably, the unsaturated polyester resin comprising ethylenicunsaturations such as di-acid ethylenic unsaturations such as2-butenedioic acid ethylenic unsaturations is obtainable from at leastthe following monomers: unsaturated di-acid for example any isomer of2-butenedioic acid, 2-methyl-2-butenedioic acid, itaconic acid,derivatives thereof and/or mixtures thereof, terephthalic acid,neopentylglycol and/or propylene glycol. Trifunctional monomers such astrimethylolpropane may be used in order to obtain branched unsaturatedpolyester resin comprising ethylenic unsaturations such as di-acidethylenic unsaturations such as 2-butenedioic acid ethylenicunsaturations.

Most preferably, the UR is an unsaturated polyester resin comprising2-butenedioic acid ethylenic unsaturations.

The disclosures and any and all preferments concerning the ethylenicunsaturations, the M_(n), T_(g), WPU, AV, OHV, viscosity of the URpresented here below till the end of section 1.1, are also meant to bedisclosed for and apply equally for each one of acrylic resin,polyurethane, epoxy resin, polyamide, polyesteramide, polycarbonate,polyurea and polyester resin e.g. for an unsaturated polyester resin,for an unsaturated polyester resin comprising ethylenic unsaturationssuch as an acrylated polyester resin, unsaturated polyester resincomprising di-acid ethylenic unsaturations, for an unsaturated polyesterresin comprising 2-butenedioic acid ethylenic unsaturations.

Preferably, the ethylenic unsaturations of the UR are di-acid ethylenicunsaturations. More preferably, the ethylenic unsaturations of the URare 2-butenedioic acid ethylenic unsaturations.

Preferably, the UR has a M_(n) of at least 800, more preferably of atleast 1000, even more preferably of at least 1500, most preferably of atleast 1800, especially of at least 2000, more especially of at least2200 Da. Preferably, the UR has a M_(n) of at most 20000, morepreferably of at most 10000, even more preferably of at most 9000, mostpreferably of at most 8000, especially of at most 7000, more especiallyof at most 6000, most especially of at most 5000 Da. Preferably, the URhas a M_(n) of at least 1000 and of at most 10000, more preferably of atleast 2000 and of at most 8000 Da.

Preferably, the UR has a WPU of at least 250, more preferably of atleast 300, even more preferably of at least 350, most preferably of atleast 400, most preferably of at least 450, especially of at least 500g/mol. The UR has a WPU of at most 2200, more preferably of at most1650, even more preferably of at most 1450, most preferably of at most1350, especially of at most 1200 g/mol. Preferably the WPU of UR rangesfrom 250 to 2200, more preferably from 450 to 1350 g/mol.

Preferably the UR has a glass transition temperature of at least 20,more preferably of at least 25, even more preferably of at least 30,most preferably of at least 40° C. Preferably, the UR has a glasstransition temperature of at most 120, more preferably of at most 110,even more preferably of at most 100, most preferably of at most 90,especially of at most 80, more especially of at most 75, most especiallyof at most 70, for example of at most 65, for example of at most 60° C.Preferably the UR has a glass transition temperature of at least 20 andat most 120, more preferably of at least 30 and at most 100, even morepreferably of at least 35 and at most 90, most preferably of at least 40and at most 75° C. Preferably, the UR has a glass transition temperatureof at least 40 and of at most 75° C.

Preferably the UR has a viscosity of at most 150, more preferably of atmost 120, even more preferably of at most 100, most preferably of atmost 80, especially of at most 60, more especially of at most 40, mostespecially of at most 20, for example of at most 15 Pa·s. Preferably theUR has a viscosity of at least 0.001, more preferably of at least 0.1,even more preferably of at least 0.5, most preferably of at least 1,especially of at least 2 Pa·s. Preferably the UR has a viscosity of atleast 0.001 and at most 40 Pa·s, more preferably of at least 0.05 and atmost 20 Pa·s.

If the UR has carboxyl groups, then the acid value (AV) of the UR ispreferably at least 0 and at most 60, more preferably at least 0.05 andat most 50, even more preferably of at least 0.1 and at most 20, mostpreferably at least 0.1 and at most 10 mg KOH/g UR.

If the UR has hydroxyl groups, then the hydroxyl value (OHV) of the URis preferably at least 0.1 and at most 80, more preferably at least 5and at most 75, even more preferably at least 8 and at most 70, mostpreferably at least 10 and at most 60 mg KOH/g UR.

1.2 the Component B of the TPCC of the Invention

The terms ‘component B’ and ‘B’ are used herein interchangeably.

The TPCC of the invention comprises component B wherein component Brepresents one or more curing agents selected from the group consistingof vinyl urethanes, vinyl functionalized urethane resins and mixturesthereof, wherein at least one curing agent is curing agent A which isselected from the group consisting of i), ii) and iii):

-   -   i) one or more crystalline VU-c each of which is a crystalline        vinyl urethane having a melting enthalpy ΔH_(m)≥35 J/g and one        or more melting temperatures (T_(m)) wherein any and all of the        T_(m) of the one or more crystalline VU-c are in the region of        from and including 30 up to and including 80° C., and    -   ii) one or more crystalline VFUR-c each of which is a        crystalline vinyl functionalized urethane resin having a melting        enthalpy ΔH_(m)≥35 J/g and one or more melting temperatures        (T_(m)) wherein any and all of the T_(m) of the one or more        crystalline VFUR-c are in the region of from and including 30 up        to and including 80° C., and    -   iii) mixtures of crystalline VU-c and crystalline VFUR-c,        wherein the ΔH_(m) and T_(m) is each measured via Differential        Scanning Calorimetry (DSC) according to the description.

By ‘curing agent’ is meant a compound selected from the group consistingof vinyl urethanes, vinyl functionalized urethane resins and mixturesthereof.

The vinyl urethane (VU) may be amorphous or crystalline. An example of aVU is Uralac® P3307 which is a crystalline VU having a T_(m) of 100° C.

The vinyl functionalized urethane resin (VFUR) may be amorphous orcrystalline.

Preferably the vinyl urethane (VU)—whether amorphous or crystalline—hasa M_(n) of at least 400 and of at most 20000 Da, and a WPU of at least100 and of at most 2000 g/mol; and the vinyl functionalized urethaneresin (VFUR)—whether amorphous or crystalline—has a M_(n) of at least400 and of at most 20000 Da, and a WPU of at least 100 and of at most2000 g/mol.

If the VU has a T_(m), then its T_(m) is preferably at least 20 and atmost 120° C.

If the VFUR has a T_(m), then its T_(m) is preferably at least 20 and atmost 120° C.

If the VFUR has a T_(g), then its T_(g) is preferably at least −80 andat most 100, more preferably at most 80° C.

Preferably the crystalline VU-c is selected from the group consisting ofcrystalline VEU-c, crystalline VESU-c, and crystalline VEESU-c; morepreferably the crystalline VU-c is selected from the group consisting ofcrystalline VEU-c, and crystalline VESU-c; most preferably thecrystalline VU-c is selected from the group consisting of crystallineVEU-c; especially the crystalline VU-c is selected from the groupconsisting of diethylene glycol divinyl ether urethane, triethyleneglycol divinyl ether urethane and mixtures thereof; more especially thecrystalline VU-c is diethylene glycol divinyl ether urethane; mostespecially the crystalline VU-c is triethylene glycol divinyl etherurethane.

Preferably the crystalline VFUR-c is selected from the group consistingof crystalline VEFUR-c, crystalline VESFUR-c, and crystalline VEESFUR-c;more preferably the crystalline VFUR-c is selected from the groupconsisting of crystalline VEFUR-c, and crystalline VESFUR-c; mostpreferably the crystalline VFUR-c is selected from the group consistingof crystalline VEFUR-c.

Preferably, the TPCC of the invention comprises component B whereincomponent B represents one or more curing agents, wherein at least onecuring agent is curing agent A which is selected from the groupconsisting of i), ii) and iii):

-   -   i) one or more crystalline VU-c each of which is a crystalline        vinyl urethane having a melting enthalpy ΔH_(m)≥35 J/g and one        or more melting temperatures (T_(m)) wherein any and all of the        T_(m) of the one or more crystalline VU-c are in the region of        from and including 30 up to and including 80° C., and wherein        the crystalline VU-c is selected from the group consisting of        crystalline VEU-c, crystalline VESU-c, and crystalline VEESU-c;        more preferably from the group consisting of crystalline VEU-c,        and crystalline VESU-c; most preferably from the group        consisting of crystalline VEU-c;    -   especially from the group consisting of diethylene glycol        divinyl ether urethane, triethylene glycol divinyl ether        urethane and mixtures thereof; more especially is diethylene        glycol divinyl ether urethane; most especially the crystalline        VU-c is triethylene glycol divinyl ether urethane, and    -   ii) one or more crystalline VFUR-c each of which is a        crystalline vinyl functionalized urethane resin having a melting        enthalpy ΔH_(m)≥35 J/g and one or more melting temperatures        (T_(m)) wherein any and all of the T_(m) of the one or more        crystalline VFUR-c are in the region of from and including 30 up        to and including 80° C., and wherein the crystalline VFUR-c is        selected from the group consisting of crystalline VEFUR-c,        crystalline VESFUR-c, and crystalline VEESFUR-c; more preferably        the crystalline VFUR-c is selected from the group consisting of        crystalline VEFUR-c, and crystalline VESFUR-c; most preferably        the crystalline VFUR-c is selected from the group consisting of        crystalline VEFUR-c, and    -   iii) mixtures of crystalline VU-c and crystalline VFUR-c,        wherein the ΔH_(m) and T_(m) is each measured via Differential        Scanning Calorimetry (DSC) according to the description.

Preferably, the TPCC of the invention comprises component B whereincomponent B represents one or more curing agents, wherein at least onecuring agent is curing agent A which is one or more crystalline VU-ceach of which is a crystalline vinyl urethane having a melting enthalpyΔH_(m)≥35 J/g and one or more melting temperatures (T_(m)) wherein anyand all of the T_(m) of the one or more crystalline VU-c are in theregion of from and including 30 up to and including 80° C., and whereinthe crystalline VU-c is a crystalline VEU-c, and wherein the ΔH_(m) andT_(m) is each measured via Differential Scanning Calorimetry (DSC)according to the description.

Preferably, the TPCC of the invention comprises component B whereincomponent B represents one or more curing agents, wherein at least onecuring agent is curing agent A which is one or more crystalline VU-ceach of which is a crystalline vinyl urethane having a melting enthalpyΔH_(m)≥35 J/g and one or more melting temperatures (T_(m)) wherein anyand all of the T_(m) of the one or more crystalline VU-c are in theregion of from and including 30 up to and including 80° C. (preferablyin the region of from and including 30 up to and including 78° C., morepreferably in the region of form and including 45 up to and including77° C.), and wherein the crystalline VU-c is selected from the groupconsisting of diethylene glycol divinyl ether urethane, triethyleneglycol divinyl ether urethane and mixtures thereof; more especially thecrystalline VU-c is diethylene glycol divinyl ether urethane; mostespecially the crystalline VU-c is triethylene glycol divinyl etherurethane, and wherein the ΔH_(m) and T_(m) is each measured viaDifferential Scanning Calorimetry (DSC) according to the description.

Preferably, in the TPCC of the invention the component B is present inan amount of at least 4 and at most 90, more preferably in an amount ofat least 10 and at most 85, even more preferably in an amount of atleast 15 and at most 60, most preferably in an amount of at least 16 andat most 55 pph of A and B.

Preferably, in the TPCC of the invention the curing agent A is presentin an amount of at least 5, more preferably at least 10, even morepreferably at least 20, most preferably at least 30, especially at least40, more especially at least 50, most especially at least 60, forexample at least 70, for example at least 80, for example at least 90,for example at least 94, for example at least 95, for example at least96, for example at least 97, for example at least 98, for example atleast 99, for example at least 99.1, for example at least 99.2, forexample at least 99.3, for example at least 99.4, for example at least99.5, for example at least 99.6, for example at least 99.7, for exampleat least 99.8, for example at least 99.9, for example 100 pph of B.Preferably in the TPCC of the invention the curing agent A is present inan amount of at least 98, more preferably in an amount of at least 99pph of B.

Preferably, the K is at most 9, preferably at most 8, more preferably atmost 7, even more preferably at most 6, most preferably at most 5,especially at most 4, more especially at most 3, even more especially atmost 2.8, most especially at most 2.6, for example at most 2.5.Preferably, the K is at least 0.1, more preferably at least 0.2, evenmore preferably at least 0.3, most preferably at least 0.4, especiallyat least 0.5, more especially at least 0.6, most especially at least0.7, for example at least 0.8. Preferably the K is at least 0.3 and atmost 9, more preferably K is at least 0.5 and at most 4, most preferablyK is at least 0.6 and at most 3, especially K is at least 0.8 and atmost 2.8, more especially K is at least 0.9 and at most 2.6, mostespecially K is at least 0.95 and at most 2.5, for example K is at least0.95 and at most 3, for example K is at least 0.8 and at most 2.5.

The curing agent A may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45, most preferably at most 40,especially at most 35° C., lower than its T_(m), or lower than itshighest T_(m) if the curing agent A has more than one T_(m). Preferablythe curing agent A has a crystallization temperature (T_(c)) of at least0 and of at most 75, more preferably of at least 10 and of at most 75,even more preferably of at least 10 and at most 72, most preferably ofat least 10 and at most 70, especially of at least 10 and at most 68,more especially of at least 10 and at most 66, for example of at least10 and at most 65, for example of at least 15 and at most 62, forexample of at least 20 and at most 60° C.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.2 and in sub-sections 1.2.1 and 1.2.2 can be combined witheach other and with any other feature, element, component, embodiment,aspect, range and especially any preferred feature, preferred element,preferred embodiment, preferred aspect, preferred range, preferredcombination of ranges, preferments, embodiments and aspects of theinvention as these are disclosed in the entire application.

1.2.1 The crystalline VU-c of curing agent A By ‘crystalline VU-c’ ismeant a crystalline vinyl urethane having a melting enthalpy ΔH_(m)≥35J/g, and one or more melting temperatures (T_(m)) wherein any and all ofthe T_(m) of the one or more crystalline VU-c are in the region of fromand including 30 up to and including 80° C. Preferably the crystallineVU-c has a melting enthalpy ΔH_(m)≥40, more preferably ≥50, even morepreferably ≥60, most preferably ≥70, especially ≥80, more especially≥90, most especially ≥100, for example ≥110, for example ≥120 J/g.

Preferably the crystalline VU-c has one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the one or more crystallineVU-c are in the region of from and including 40 up to and including 80°C., more preferably of from and including 45 up to and including 80° C.,most preferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VU-c has a M_(n) of at least 400 and of atmost 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VU-c has a M_(n) of at least 400 and of atmost 20000 Da, more preferably of at least 450 and of at most 10000 Da,most preferably of at least 500 and of at most 7000 Da, especially of atleast 550 and of at most 5000, more especially of at least 575 and of atmost 3000 Da, most especially of at least 600 and of at most 2000 Da,for example of at least 660 and of at most 2000 Da, for example of atleast 660 and of at most 1500 Da, for example of at least 660 and of atmost 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VU-c has a M_(n) of at least 400 and of atmost 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VU-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VU-c has a WPU ofat most 2000, more preferably at most 1500, even more preferably at most1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VU-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

The crystalline VU-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m),or lower than its highest T_(m) if the crystalline VU-c has more thanone T_(m). Preferably the crystalline VU-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

Examples of crystalline VU-c include but are not limited to diethyleneglycol divinyl ether urethane and triethylene glycol divinyl etherurethane.

Obviously, crystalline VU-c is a sub-class of vinyl urethanes. Forexample Uralac® P3307 is a VU (in specific a crystalline VU) but it isnot a crystalline VU-c.

Preferably the crystalline VU-c is selected from the group consisting ofcrystalline VEU-c, crystalline VESU-c, and crystalline VEESU-c; morepreferably the crystalline VU-c is selected from the group consisting ofcrystalline VEU-c, and crystalline VESU-c; most preferably thecrystalline VU-c is selected from the group consisting of crystallineVEU-c; especially the crystalline VU-c is selected from the groupconsisting of diethylene glycol divinyl ether urethane, triethyleneglycol divinyl ether urethane and mixtures thereof; more especially thecrystalline VU-c is diethylene glycol divinyl ether urethane; mostespecially the crystalline VU-c is triethylene glycol divinyl etherurethane.

The formulae of diethylene glycol divinyl ether urethane and triethyleneglycol divinyl ether urethane are as shown below:

By ‘crystalline VEU-c’ is meant a crystalline vinyl ether urethanehaving a melting enthalpy ΔH_(m)≥35 J/g, and one or more meltingtemperatures (T_(m)) wherein any and all of the T_(m) of the one or morecrystalline VEU-c are in the region of from and including 30 up to andincluding 80° C. A crystalline VEU-c is a sub-class of a crystallineVU-c.

Preferably the crystalline VEU-c has a melting enthalpy ΔH_(m)≥40, morepreferably ≥50, even more preferably ≥60, most preferably ≥70,especially ≥80, more especially ≥90, most especially ≥100, for example≥110, for example ≥120 J/g.

Preferably the crystalline VEU-c has one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the one or more crystallineVEU-c are in the region of from and including 40 up to and including 80°C., more preferably of from and including 45 up to and including 80° C.,most preferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VEU-c has a M_(n) of at least 400 and of atmost 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VEU-c has a M_(n) of at least 400 and of atmost 20000 Da, more preferably of at least 450 and of at most 10000 Da,most preferably of at least 500 and of at most 7000 Da, especially of atleast 550 and of at most 5000, more especially of at least 575 and of atmost 3000 Da, most especially of at least 600 and of at most 2000 Da,for example of at least 660 and of at most 2000 Da, for example of atleast 660 and of at most 1500 Da, for example of at least 660 and of atmost 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VEU-c has a M_(n) of at least 400 and of atmost 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VEU-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VEU-c has a WPUof at most 2000, more preferably at most 1500, even more preferably atmost 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VEU-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

Examples of crystalline VEU-c include but are not limited to diethyleneglycol divinyl ether urethane and triethylene glycol divinyl etherurethane.

The crystalline VEU-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m),or lower than its highest T_(m) if the crystalline VEU-c has more thanone T_(m). Preferably the crystalline VEU-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

By ‘crystalline VESU-c’ is meant a crystalline vinyl ester urethanehaving a melting enthalpy ΔH_(m)≥35 J/g, and one or more meltingtemperatures (T_(m)) wherein any and all of the T_(m) of the one or morecrystalline VESU-c are in the region of from and including 30 up to andincluding 80° C. A crystalline VESU-c is a sub-class of a crystallineVU-c. Preferably the crystalline VESU-c has a melting enthalpyΔH_(m)≥40, more preferably ≥50, even more preferably ≥60, mostpreferably ≥70, especially ≥80, more especially ≥90, most especially≥100, for example ≥110, for example ≥120 J/g.

Preferably the crystalline VESU-c has one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the one or more crystallineVESU-c are in the region of from and including 40 up to and including80° C., more preferably of from and including 45 up to and including 80°C., most preferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VESU-c has a M_(n) of at least 400 and of atmost 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VESU-c has a M_(n) of at least 400 and of atmost 20000 Da, more preferably of at least 450 and of at most 10000 Da,most preferably of at least 500 and of at most 7000 Da, especially of atleast 550 and of at most 5000, more especially of at least 575 and of atmost 3000 Da, most especially of at least 600 and of at most 2000 Da,for example of at least 660 and of at most 2000 Da, for example of atleast 660 and of at most 1500 Da, for example of at least 660 and of atmost 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VESU-c has a M_(n) of at least 400 and of atmost 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VESU-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VESU-c has a WPUof at most 2000, more preferably at most 1500, even more preferably atmost 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VESU-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

The crystalline VESU-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m),or lower than its highest T_(m) if the crystalline VESU-c has more thanone T_(m). Preferably the crystalline VESU-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

By ‘crystalline VEESU-c’ is meant a crystalline vinyl (ether-ester)urethane having a melting enthalpy ΔH_(m)≥35 J/g, and one or moremelting temperatures (T_(m)) wherein any and all of the T_(m) of the oneor more crystalline VEESU-c are in the region of from and including 30up to and including 80° C. A crystalline VEESU-c is a sub-class of acrystalline VU-c. Preferably the crystalline VEESU-c has a meltingenthalpy ΔH_(m)≥40, more preferably ≥50, even more preferably ≥60, mostpreferably ≥70, especially ≥80, more especially ≥90, most especially≥100, for example ≥110, for example ≥120 J/g.

Preferably the crystalline VEESU-c has one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the one or more crystallineVEESU-c are in the region of from and including 40 up to and including80° C., more preferably of from and including 45 up to and including 80°C., most preferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VEESU-c has a M_(n) of at least 400 and of atmost 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VEESU-c has a M_(n) of at least 400 and of atmost 20000 Da, more preferably of at least 450 and of at most 10000 Da,most preferably of at least 500 and of at most 7000 Da, especially of atleast 550 and of at most 5000, more especially of at least 575 and of atmost 3000 Da, most especially of at least 600 and of at most 2000 Da,for example of at least 660 and of at most 2000 Da, for example of atleast 660 and of at most 1500 Da, for example of at least 660 and of atmost 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VEESU-c has a M_(n) of at least 400 and of atmost 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VEESU-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VEESU-c has a WPUof at most 2000, more preferably at most 1500, even more preferably atmost 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VEESU-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

The crystalline VEESU-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m),or lower than its highest T_(m) if the crystalline VEESU-c has more thanone T_(m). Preferably the crystalline VEESU-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.2.1 can be combined with each other and with any otherfeature, element, component, embodiment, aspect, range and especiallyany preferred feature, preferred element, preferred embodiment,preferred aspect, preferred range, preferred combination of ranges,preferments, embodiments and aspects of the invention as these aredisclosed in the entire application.

1.2.2 the Crystalline VFUR-c of Curing Agent A

By ‘crystalline VFUR-c’ is meant a crystalline vinyl functionalizedurethane resin having a melting enthalpy ΔH_(m)≥35 J/g, and one or moremelting temperatures (T_(m)) wherein any and all of the T_(m) of the oneor more crystalline VFUR-c are in the region of from and including 30 upto and including 80° C. Preferably the crystalline VFUR-c has a meltingenthalpy ΔH_(m)≥40, more preferably ≥50, even more preferably ≥60, mostpreferably ≥70, especially ≥80, more especially ≥90, most especially≥100, for example ≥110, for example ≥120, J/g. Preferably thecrystalline VFUR-c has one or more melting temperatures (T_(m)) whereinany and all of the T_(m) of the one or more crystalline VFUR-c are inthe region of from and including 40 up to and including 80° C., morepreferably of from and including 45 up to and including 80° C., mostpreferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VFUR-c has a T_(g) of at least −80 and atmost 75° C., more preferably of at least −80 and at most 70° C., evenmore preferably of at least −80 and at most 60° C., most preferably ofat least −80 and at most 50° C., especially of at least −80 and at most40° C., more especially of at least −80 and at most 30° C., mostespecially of at least −80 and at most 20° C., for example of at least−80 and at most 10° C., for example of at least −80 and at most 0° C.,for example of at least −80 and at most −10° C., for example of at least−80 and at most −20° C.

Preferably the crystalline VFUR-c has a M_(n) of at least 400 and of atmost 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VFUR-c has a M_(n) of at least 400 and of atmost 20000 Da, more preferably of at least 450 and of at most 10000 Da,most preferably of at least 500 and of at most 7000 Da, especially of atleast 550 and of at most 5000, more especially of at least 575 and of atmost 3000 Da, most especially of at least 600 and of at most 2000 Da,for example of at least 660 and of at most 2000 Da, for example of atleast 660 and of at most 1500 Da, for example of at least 660 and of atmost 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VFUR-c has a M_(n) of at least 400 and of atmost 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VFUR-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VFUR-c has a WPUof at most 2000, more preferably at most 1500, even more preferably atmost 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VFUR-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

Obviously, crystalline VFUR-c is a sub-class of VFUR.

Preferably the crystalline VFUR-c is selected from the group consistingof crystalline VEFUR-c, crystalline VESFUR-c, and crystalline VEESFUR-c;more preferably the crystalline VFUR-c is selected from the groupconsisting of crystalline VEFUR-c, and crystalline VESFUR-c; mostpreferably the crystalline VFUR-c is selected from the group consistingof crystalline VEFUR-c.

The crystalline VFUR-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m),or lower than its highest T_(m) if the crystalline VFUR-c has more thanone T_(m). Preferably the crystalline VFUR-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

By ‘crystalline VEFUR-c’ is meant a crystalline vinyl etherfunctionalized urethane resin having a melting enthalpy ΔH_(m)≥35 J/g,and one or more melting temperatures (T_(m)) wherein any and all of theT_(m) of the one or more crystalline VEFUR-c are in the region of fromand including 30 up to and including 80° C. A crystalline VEFUR-c is asub-class of a crystalline VFUR-c. Preferably the crystalline VEFUR-chas a melting enthalpy ΔH_(m)≥40, more preferably ≥50, even morepreferably ≥60, most preferably ≥70, especially ≥80, more especially≥90, most especially ≥100, for example ≥110, for example ≥120, J/g.Preferably the crystalline VEFUR-c has one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the one or more crystallineVEFUR-c are in the region of from and including 40 up to and including80° C., more preferably of from and including 45 up to and including 80°C., most preferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VEFUR-c has a T_(g) of at least −80 and atmost 75° C., more preferably of at least −80 and at most 70° C., evenmore preferably of at least −80 and at most 60° C., most preferably ofat least −80 and at most 50° C., especially of at least −80 and at most40° C., more especially of at least −80 and at most 30° C., mostespecially of at least −80 and at most 20° C., for example of at least−80 and at most 10° C., for example of at least −80 and at most 0° C.,for example of at least −80 and at most −10° C., for example of at least−80 and at most −20° C.

Preferably the crystalline VEFUR-c has a M_(n) of at least 400 and of atmost 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VEFUR-c has a M_(n) of at least 400 and of atmost 20000 Da, more preferably of at least 450 and of at most 10000 Da,most preferably of at least 500 and of at most 7000 Da, especially of atleast 550 and of at most 5000, more especially of at least 575 and of atmost 3000 Da, most especially of at least 600 and of at most 2000 Da,for example of at least 660 and of at most 2000 Da, for example of atleast 660 and of at most 1500 Da, for example of at least 660 and of atmost 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VEFUR-c has a M_(n) of at least 400 and of atmost 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VEFUR-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VEFUR-c has a WPUof at most 2000, more preferably at most 1500, even more preferably atmost 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VEFUR-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

The crystalline VEFUR-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m),or lower than its highest T_(m) if the crystalline VEFUR-c has more thanone T_(m). Preferably the crystalline VEFUR-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

By ‘crystalline VESFUR-c’ is meant a crystalline vinyl esterfunctionalized urethane resin having a melting enthalpy ΔH_(m)≥35 J/g,and one or more melting temperatures (T_(m)) wherein any and all of theT_(m) of the one or more crystalline VESFUR-c are in the region of fromand including 30 up to and including 80° C. A crystalline VESFUR-c is asub-class of a crystalline VFUR-c. Preferably the crystalline VESFUR-chas a melting enthalpy ΔH_(m)≥40, more preferably ≥50, even morepreferably ≥60, most preferably ≥70, especially ≥80, more especially≥90, most especially ≥100, for example ≥110, for example ≥120, J/g.Preferably the crystalline VESFUR-c has one or more melting temperatures(T_(m)) wherein any and all of the T_(m) of the one or more crystallineVESFUR-c are in the region of from and including 40 up to and including80° C., more preferably of from and including 45 up to and including 80°C., most preferably of from and including 50 up to and including 80° C.,especially of from and including 30 up to and including 78° C., moreespecially of from and including 40 up to and including 78° C., mostespecially of from and including 45 up to and including 78° C., forexample of from and including 50 up to and including 78° C., for exampleof from and including 30 up to and including 77° C., for example of fromand including 40 up to and including 77° C., for example of from andincluding 45 up to and including 77° C., for example of from andincluding 50 up to and including 77° C.

Preferably the crystalline VESFUR-c has a T_(g) of at least −80 and atmost 75° C., more preferably of at least −80 and at most 70° C., evenmore preferably of at least −80 and at most 60° C., most preferably ofat least −80 and at most 50° C., especially of at least −80 and at most40° C., more especially of at least −80 and at most 30° C., mostespecially of at least −80 and at most 20° C., for example of at least−80 and at most 10° C., for example of at least −80 and at most 0° C.,for example of at least −80 and at most −10° C., for example of at least−80 and at most −20° C.

Preferably the crystalline VESFUR-c has a M_(n) of at least 400 and ofat most 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VESFUR-c has a M_(n) of at least 400 and ofat most 20000 Da, more preferably of at least 450 and of at most 10000Da, most preferably of at least 500 and of at most 7000 Da, especiallyof at least 550 and of at most 5000, more especially of at least 575 andof at most 3000 Da, most especially of at least 600 and of at most 2000Da, for example of at least 660 and of at most 2000 Da, for example ofat least 660 and of at most 1500 Da, for example of at least 660 and ofat most 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VESFUR-c has a M_(n) of at least 400 and ofat most 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VESFUR-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VESFUR-c has aWPU of at most 2000, more preferably at most 1500, even more preferablyat most 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VESFUR-c is at most 30, morepreferably at most 25, even more preferably at most 20, most preferablyat most 15, especially at most 10, more especially at most 8, mostespecially at most 6, for example at most 5, for example at most 4, forexample at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

The crystalline VESFUR-c may have a T_(c) which is lower than its T_(m).Preferably the T_(c) of the curing agent is at most 55, more preferablyat most 50, even more preferably at most 45° C., lower than its T_(m) orlower than its highest T_(m) if the crystalline VESFUR-c has more thanone T_(m). Preferably the crystalline VESFUR-c has a crystallizationtemperature (T_(c)) of at least 0 and of at most 75, more preferably ofat least 10 and of at most 75, even more preferably of at least 10 andat most 72, most preferably of at least 10 and at most 70, especially ofat least 10 and at most 68, more especially of at least 10 and at most66, for example of at least 10 and at most 65, for example of at least15 and at most 62, for example of at least 20 and at most 60° C.

By ‘crystalline VEESFUR-c’ is meant a crystalline vinyl (ether-ester)functionalized urethane resin having a melting enthalpy ΔH_(m)≥35 J/g,and one or more melting temperatures (T_(m)) wherein any and all of theT_(m) of the one or more crystalline VEESFUR-c are in the region of fromand including 30 up to and including 80° C. A crystalline VEESFUR-c is asub-class of a crystalline VFUR-c. Preferably the crystalline VEESFUR-chas a melting enthalpy ΔH_(m)≥40, more preferably ≥50, even morepreferably ≥60, most preferably ≥70, especially ≥80, more especially≥90, most especially ≥100, for example ≥110, for example ≥120, J/g.Preferably the crystalline VEESFUR-c has one or more meltingtemperatures (T_(m)) wherein any and all of the T_(m) of the one or morecrystalline VEESFUR-c are in the region of from and including 40 up toand including 80° C., more preferably of from and including 45 up to andincluding 80° C., most preferably of from and including 50 up to andincluding 80° C., especially of from and including 30 up to andincluding 78° C., more especially of from and including 40 up to andincluding 78° C., most especially of from and including 45 up to andincluding 78° C., for example of from and including 50 up to andincluding 78° C., for example of from and including 30 up to andincluding 77° C., for example of from and including 40 up to andincluding 77° C., for example of from and including 45 up to andincluding 77° C., for example of from and including 50 up to andincluding 77° C.

Preferably the crystalline VEESFUR-c has a T_(g) of at least −80 and atmost 75° C., more preferably of at least −80 and at most 70° C., evenmore preferably of at least −80 and at most 60° C., most preferably ofat least −80 and at most 50° C., especially of at least −80 and at most40° C., more especially of at least −80 and at most 30° C., mostespecially of at least −80 and at most 20° C., for example of at least−80 and at most 10° C., for example of at least −80 and at most 0° C.,for example of at least −80 and at most −10° C., for example of at least−80 and at most −20° C.

Preferably the crystalline VEESFUR-c has a M_(n) of at least 400 and ofat most 20000 Da, and a WPU of at least 100 and of at most 2000 g/mol.Preferments of these ranges are detailed herein.

Preferably the crystalline VEESFUR-c has a M_(n) of at least 400 and ofat most 20000 Da, more preferably of at least 450 and of at most 10000Da, most preferably of at least 500 and of at most 7000 Da, especiallyof at least 550 and of at most 5000, more especially of at least 575 andof at most 3000 Da, most especially of at least 600 and of at most 2000Da, for example of at least 660 and of at most 2000 Da, for example ofat least 660 and of at most 1500 Da, for example of at least 660 and ofat most 1200 Da, for example of at least 660 and of at most 1000 Da.Preferably the crystalline VEESFUR-c has a M_(n) of at least 400 and ofat most 5000 Da, more preferably of at least 500 and of at most 3000 Da,most preferably of at least 600 and of at most 2000 Da, especially of atleast 660 and of at most 1500, more especially of at least 660 and of atmost 1200 Da.

Preferably, the crystalline VEESFUR-c has a WPU of at least 100, morepreferably at least 120, even more preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155, most especially at least 160, for example at least 170, forexample at least 190 g/mol. Preferably the crystalline VEESFUR-c has aWPU of at most 2000, more preferably at most 1500, even more preferablyat most 1200, most preferably at most 1000, especially at most 900, moreespecially at most 800, most especially at most 700, for example at most600, for example at most 500, for example at most 400, for example atmost 380, for example at most 370, for example at most 350, for exampleat most 300, for example at most 280, for example at most 260 g/mol.

Preferably the viscosity of the crystalline VEESFUR-c is at most 30,more preferably at most 25, even more preferably at most 20, mostpreferably at most 15, especially at most 10, more especially at most 8,most especially at most 6, for example at most 5, for example at most 4,for example at most 3, for example at most 2, for example at most 1, forexample at most 0.5, for example at most 0.2, for example at most 0.1Pa·s.

The crystalline VEESFUR-c may have a T_(c) which is lower than itsT_(m). Preferably the T_(c) of the curing agent is at most 55, morepreferably at most 50, even more preferably at most 45° C., lower thanits T_(m), or lower than its highest T_(m) if the crystalline VEESFUR-chas more than one T_(m). Preferably the crystalline VEESFUR-c has acrystallization temperature (T_(c)) of at least 0 and of at most 75,more preferably of at least 10 and of at most 75, even more preferablyof at least 10 and at most 72, most preferably of at least 10 and atmost 70, especially of at least 10 and at most 68, more especially of atleast 10 and at most 66, for example of at least 10 and at most 65, forexample of at least 15 and at most 62, for example of at least 20 and atmost 60° C.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.2.2 can be combined with each other and with any otherfeature, element, component, embodiment, aspect, range and especiallyany preferred feature, preferred element, preferred embodiment,preferred aspect, preferred range, preferred combination of ranges,preferments, embodiments and aspects of the invention as these aredisclosed in the entire application.

1.2.3 Methods of Preparation of a VU or a VFUR

A VU (including any sub-class such as a crystalline VU-c) may beprepared from

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups and said        compound B is selected from the group consisting of compounds        comprising vinyl ether groups and compounds comprising vinyl        ester groups and compounds comprising vinyl ether and vinyl        ester groups; and preferably the hydroxyl groups of compound B        are able to react with the isocyanate groups of compound A.        Examples of preparing a VU are given in the Examples.

In case the VU is a vinyl ether urethane such as for example acrystalline VEU-c, then said vinyl ether urethane may be prepared from:

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups and vinyl ether        groups; and preferably the hydroxyl groups of compound B are        able to react with the isocyanate groups of compound A.

In case the VU is a vinyl ester urethane such as for example acrystalline VESU-c, then said vinyl ester urethane may be prepared from:

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups and vinyl ester        groups; and preferably the hydroxyl groups of compound B are        able to react with the isocyanate groups of compound A.

In case the VU is a vinyl(ether-ester) urethane such as for example acrystalline VEESU-c, then said vinyl(ether-ester) urethane may beprepared from:

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups, vinyl ether        groups and vinyl ester groups; and preferably the hydroxyl        groups of compound B are able to react with the isocyanate        groups of compound A.

A VFUR (including any sub-class such as a crystalline VFUR-c) may beprepared from

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups and said        compound B is selected from the group consisting of compounds        comprising vinyl ether groups and compounds comprising vinyl        ester groups and compounds comprising vinyl ether and vinyl        ester groups; and preferably the hydroxyl groups of compound B        are able to react with the isocyanate groups of compound A; and    -   at least an organic compound C comprising hydroxyl groups which        are able to react with the isocyanate groups of compound A.

In case the VFUR is a vinyl ether functionalized urethane resin (VEFUR),then the VEFUR may be prepared from:

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups and vinyl ether        groups; and preferably the hydroxyl groups of compound B are        able to react with the isocyanate groups of compound A; and    -   at least an organic compound C comprising hydroxyl groups which        are able to react with the isocyanate groups of compound A.

In case the VFUR is a vinyl ester functionalized urethane resin(VESFUR), then the VESFUR may be prepared from:

-   -   at least a compound A comprising isocyanate groups; and    -   at least a compound B comprising hydroxyl groups and vinyl ester        groups; and preferably the hydroxyl groups of compound B are        able to react with the isocyanate groups of compound A; and    -   at least an organic compound C comprising hydroxyl groups which        are able to react with the isocyanate groups of compound A.

In case the VFUR is a vinyl(ether-ester) functionalized urethane resin,then the VEESFUR may be prepared from at least a compound A comprisingisocyanate groups; and

-   -   at least a compound B comprising hydroxyl groups, vinyl ether        groups and vinyl ester groups; and preferably the hydroxyl        groups of compound B are able to react with the isocyanate        groups of compound A; and    -   at least an organic compound C comprising hydroxyl groups which        are able to react with the isocyanate groups of compound A.

The vinyl ether and/or vinyl ester groups may be pendant and/or terminalto the VFUR. Preferably, the vinyl ether and/or vinyl ester groups areterminal to the VFUR; in this case and depending on the existence ofvinyl ether groups and/or vinyl ester groups in the VFUR, the VFUR ismentioned herein as a vinyl ether terminated urethane resin (VFURcomprises terminal vinyl ether groups and does not comprise vinyl estergroups), or vinyl ester terminated urethane resin (VFUR comprisesterminal vinyl ester groups and does not comprise vinyl ether groups) orvinyl(ether-ester) terminated urethane resin (VFUR comprises terminalvinyl ether groups and terminal vinyl ester groups).

Broadly stated, a VU (including any sub-class such as a crystallineVU-c) may be prepared by reacting a compound A comprising isocyanategroups, for example a diisocyanate monomer with a compound B comprisinghydroxyl groups and said compound B is selected from the groupconsisting of compounds comprising vinyl ether groups (VET) andcompounds comprising vinyl ester groups (VES) and compounds comprisingvinyl ether and vinyl ester groups (VET-VES) (process 1a).

In process 1a the relative amounts of compounds A and B are chosen suchthat the sum of the hydroxyl (—OH) group equivalents of compound B isequal or in slight excess e.g. 1% excess, to the isocyanate (—NCO)groups equivalents of compound A.

Broadly stated, a VFUR (including any sub-class such as a crystallineVFUR-c) may be prepared by either:

i) reacting a compound A comprising isocyanate groups, for example apolyisocyanate with a compound B comprising hydroxyl groups and saidcompound B is selected from the group consisting of compounds comprisingvinyl ether groups (VET) and compounds comprising vinyl ester groups(VES) and compounds comprising vinyl ether and vinyl ester groups(VET-VES) and with at least an organic compound C comprising hydroxylgroups (process 2a), or by

ii) reacting a compound A comprising isocyanate groups, for example adiisocyanate monomer or a polyisocyanate with at least an organiccompound C comprising hydroxyl groups e.g. a mono-alcohol or a polyol,to form an adduct of compound A with said organic compound C, mentionedherein as “adduct”, wherein the reaction conditions will be chosen so asto form an isocyanate terminated adduct to the virtual exclusion ofhydroxyl terminated polymeric materials that can for example be achievedby the use of a molar excess of the compound A (step 1); subsequentlythe adduct is reacted with a compound B comprising hydroxyl groups andsaid compound B is selected from the group consisting of compoundscomprising vinyl ether groups (VET), compounds comprising vinyl estergroups (VES), compounds comprising vinyl ether and vinyl ester groups(VET-VES) (step 2) (process 2b).

In process 2a or 2b, the relative amounts of compounds A, B and C arechosen such that the sum of the hydroxyl (—OH) group equivalents ofcompounds B and C is equal or in slight excess e.g. 1% excess, to theisocyanate (—NCO) groups equivalents of compound A.

Preferably, the VFUR (including any sub-class such as a crystallineVFUR-c) is prepared according to process 2b.

The reaction conditions which may be employed in i) (process 1) includetemperatures that do not to exceed 120° C. Care must be taken to controlthe reaction exotherm as well. The reaction is also usually performed ina moisture free atmosphere, such as in a nitrogen atmosphere. It ispreferred that the reaction is carried out in the presence of a catalystsuch as an organotin catalyst, for example, dibutyltin dilaurate. In thereaction, a stoichiometric equivalent amount of the reactants isemployed. Thus, the reactants (Compound A, B and C) are present in a 1:1mol ratio of isocyanate to hydroxyl groups to ensure completepolymerization.

The reaction conditions which may be employed in ii) (process 2) includetemperatures in the range of 50 to 120° C. Care must be taken to controlthe urethane reaction exotherm. The reaction is also usually performedin a moisture-free atmosphere, such as in a nitrogen atmosphere. It isalso preferred that the reaction is carried out in the presence of acatalyst. A particularly preferred catalyst is one that contains tin,for example, dibutyltin dilaurate. In the reaction, a stoichiometricexcess amount of the aliphatic diisocyanate is employed. Generally, thereactants (Compound A and C) for the preparation of the adduct (step 1of process 2) are preferably present in a molar ratio (total mol ofisocyanate groups to total mol of hydroxyl groups) ranging from 40:1 to3.97:1; more preferably, said reactants are present in a molar ratiobetween 9:1 and 14:1. The reaction conditions which may be employed forstep 2 of process 2 are generally the same as those for the step 1 ofprocess 2. Usually, this step 2 will immediately follow the completionof step 1 in the same reaction vessel. Care must be taken here as wellto control the exotherm. Preferably, the total of reactants (CompoundsA, B and C) employed in steps 1 and 2 of process 2 are present in a 1:1mol ratio of isocyanate to hydroxyl groups to ensure completepolymerization and to ensure that R_(VRUF) is according to theinvention. Preferably, the amount of Compound B added during the step 2of the process 2, is chosen such that the total of reactants (CompoundsA, B and C) employed in steps 1 and 2 of process 2 are present in a 1:1mol ratio of isocyanate to hydroxyl groups to ensure completepolymerization.

The compounds A, B and C that are used in any one of the process 1a, 2aand 2b are described below.

Compound A may be an organic monomeric compound or a polymer. Preferablycompound A is an organic monomeric compound. Exemplary compounds Ainclude but are not limited to monomeric or polymeric diisocyanates forexample toluene 2,4-diisocyanate, toluene 2,6-diisocyanate (TDI, is amixture of toluene 2,4- and toluene 2,6-diisocyanate), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenyl methane diisocyanate, 2,2′-diphenylmethane diisocyanate, 1,6′-hexamethylene diisocyanate (HDI),5-isocyanato-1-(isocyanatomethy)-1,3,3-trimethylcyclohexane (isophoronediisocyanate), m-tetramethylxylene diisocyanate, dicyclohexylmethane4,4′-diisocyanate, naphthalene 1,5-diisocyanate or1,4-diisocyanatobenzene; monomeric or polymeric polyisocyanates forexample triisocyanates for exampletriphenylmethane-4,4′,4″-triisocyanate, functionalized polymers derivedfrom diisocyanates such as isocyanurates and uretdiones; and mixturesthereof. Preferably, compound A is a diisocyanate, more preferablycompound A is selected from the group consisting of toluene2,4-diisocyanate, toluene 2,6-diisocyanate, 1,6′-hexamethylenediisocyanate, isophorone diisocyanate, most preferably compound A is1,6′-hexamethylene diisocyanate.

Compound B comprises hydroxyl groups and said compound B is selectedfrom the group consisting of compounds comprising vinyl ether groups andcompounds comprising vinyl ester groups and compounds comprising vinylether and vinyl ester groups. Compound B may be an organic monomericcompound or a polymer. Preferably compound B is an organic monomericcompound. Exemplary vinyl ethers include but are not limited to mono(alcohol) functionalized vinyl ethers, for example 6-hydroxyhexyl vinylether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether,diethylene glycol monovinyl ether, triethylene glycol monovinyl ether or4-(hydroxymethyl) cyclohexyl methyl vinyl ether(1,4-cyclohexanedimethanol vinyl ether); vinyl ether polyester resinsthat can be prepared via transesterification of hydroxyl functionalpolyester resins with hydroxyl functional vinyl ethers.

The hydroxyl vinyl ethers which may be employed in making the VFURinclude those prepared by any of the methods well known to those ofordinary skill in the art. Examples of hydroxyl vinyl ethers include butare not limited to 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinylether. It is understood that other hydroxyl vinyl ethers may be used,for example, those having the general formula CH₂═CH—O—R—OH, where R isa hydrocarbylene, or CH₂—CH₂—O—CH₂—CH₂ or CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂.Preferably R is CH₂—CH₂—O—CH₂—CH₂ or CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂.

It is understood that hydroxyl vinyl esters may be used, for example,those having the general formula CH₂═CH—O—(C═O)—R—OH, where R is ahydrocarbylene, or CH₂—CH₂—O—CH₂—CH₂ or CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂.Preferably R is CH₂—CH₂—O—CH₂—CH₂ or CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂.

Exemplary vinyl esters include but are not limited to hydroxyl vinylesters and to those prepared by any of the methods well known to thoseof ordinary skill in the art. The hydroxyl vinyl esters are usuallyprepared by the reaction of acetaldehyde with acid chlorides in thepresence of tertiary amines; methods for the preparation of hydroxylvinyl esters are known in the art.

Preferably compound B is a hydroxyl vinyl ether, more preferablycompound B is selected from the group consisting of 6-hydroxyhexyl vinylether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether,diethylene glycol monovinyl ether, triethylene glycol monovinyl ether,4-(hydroxymethyl) cyclohexyl methyl vinyl ether(1,4-cyclohexanedimethanol vinyl ether), and ethoxylated hydroxybutylvinyl ether-X; more preferably compound B is selected from the groupconsisting of 6-hydroxyhexyl vinyl ether, 4-hydroxybutyl vinyl ether,2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether,triethylene glycol monovinyl ether, 4-(hydroxymethyl) cyclohexyl methylvinyl ether (1,4-cyclohexanedimethanol vinyl ether); even morepreferably compound B is selected from the group of compounds consistingof diethylene glycol monovinyl ether and triethylene glycol monovinylether; most preferably compound B is triethylene glycol monovinyl ether.

Preferably, the organic compound C is a mono-alcohol, polyol e.g.di-alcohol (diol), tri-alcohol (triol) or poly-alcohol that is analcohol having more than three hydroxyl groups per molecule, or ahydroxyl functional polymer e.g. a hydroxyl functional polyester resin.Preferably the organic compound C is selected from the group consistingof mono-alcohol, polyol, hydroxyl functional polymer; more preferablythe organic compound C is selected from the group consisting of diols,triols, polyalcohols, hydroxyl functional oligomer, hydroxyl functionalpolymer; even more preferably the organic compound C is selected fromthe group consisting of diols, triols, polyalcohols; most preferably theorganic compound C is a diol. Mono-alcohols and polyols that may be usedin i) (process 1) and/or ii) (process 2) include those selected fromcrystallizing or non-crystallizing mono-alcohols and polyols, althoughcrystallizing mono-alcohols and polyols are particularly preferred.Exemplary polyols include but are not limited to ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, 1,3-butylethyl propanediol, neopentyl glycol(2,2′-dimethyl-1,3-propanediol), 2-butyl-2-ethyl-1,3-propanediol (BEPD),2-methyl-1,3-propanediol (MP diol), 1,2-butylene glycol, 1,3-butyleneglycol, 1,4-butylene glycol, 1,3-isobutanediol, 1,2-isobutanediol,2,3-butanediol, 2-butenediol(1,4), 2,2,4-trimethyl-1,3-pentanediol,1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclopentanediol,1,6-hexanediol, 1,4-dimethoxy cylcohexane, 1,2-cyclohexanediol,1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,4,4′-methylene-bis(cyclohexanol), 4,4′-isopropylidene-bis(cyclohexanol),(hydrogenated bisphenol A) 1,4-bis(hydroxymethyl)cyclohexane,1,3-bis(hydroxyethyl) cyclohexane, 1,3-bis(hydroxypropyl) cyclohexane,1,3-bis(hydroxyisopropyl) cyclohexane, dodecanediol, xylene glycol,4,4′-isopropylidene diphenol (bisphenol A), trimethylolpropane,triethylolpropane, pentaerythritol, bisphenol A/propylene oxide adducts,hydroquinone/propylene oxide adducts, and hydroquinone/ethylene oxideadducts. Preferably, diethylene glycol or neopentyl glycol is employedin i) (process 1).

Exemplary hydroxyl functional oligomers include but are not limited tocastor oil which is a triglyceride with approximately 90% of ricinoleicacid. Exemplary hydroxyl functional polymers include but are not limitedto Uralac® P 1411, Uralac® P 1420, Uralac® P 1430, Uralac® P 1535,Uralac® P 1580, Uralac® P 1590, Uralac® P 1620, Uralac® P 1680, Uralac®P 2115, Uralac® P 4125, Uralac® P 5504 and Uralac® P 6504, and moreoverpolymers prepared via esterification from preferably crystallizingpolyols and polyacids. Preferably the hydroxyl functional polymers arehydroxyl functional polyester resins; all examples mentioned in thisparagraph are hydroxyl functional polyester resins.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.2.3 can be combined with each other and with any otherfeature, element, component, embodiment, aspect, range and especiallyany preferred feature, preferred element, preferred embodiment,preferred aspect, preferred range, preferred combination of ranges,preferments, embodiments and aspects of the invention as these aredisclosed in the entire application.

1.3 the Component C of the TPCC of the Invention

The terms ‘component C’ and ‘C’ are used herein interchangeably.

The TPCC of the invention comprises component C wherein component Crepresents one or more thermal radical initiators—preferably the one ormore thermal radical initiators are selected from the group consistingof organic peroxides, azo compounds, and mixtures thereof-, wherein atleast one thermal radical initiator is peroxydicarbonate-X present in anamount of at least 26 and at most 500 mmol/Kg A and B and wherein theperoxydicarbonate-X is selected from the group consisting ofperoxydicarbonates represented by the following formula X, and mixturesthereof,

and wherein R₁ is a C₉-C₂₂ saturated hydrocarbyl, and R₂ is a C₉-C₂₂saturated hydrocarbyl; preferably the R₁ is a C₁₀-C₁₈ saturatedhydrocarbyl, and R₂ is a C₁₀-C₁₈ saturated hydrocarbyl; more preferablythe R₁ is a C₁₀-C₁₆ saturated hydrocarbyl, and R₂ is a C₁₀-C₁₆ saturatedhydrocarbyl; even more preferably, the peroxydicarbonate-X is selectedfrom the group consisting of dimyristyl peroxydicarbonate,di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate,and mixtures thereof; most preferably, the peroxydicarbonate-X isselected from the group consisting of di(4-tert-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate, and mixtures thereof;especially the peroxydicarbonate-X is dimyristyl peroxydicarbonate; moreespecially the peroxydicarbonate-X is di(4-tert-butylcyclohexyl)peroxydicarbonate; most especially the peroxydicarbonate-X is dicetylperoxydicarbonate.

Obviously, the peroxydicarbonate-X (and its preferments) is an exampleof an organic peroxide and thus also an example of a thermal radicalinitiator.

The peroxydicarbonate-X is present in an amount of at least 26 and atmost 500 mmol/Kg A and B. Preferably the peroxydicarbonate-X is presentin an amount of at least 30 and at most 500, more preferably of at least35 and at most 500, even more preferably of at least 40 and at most 500,most preferably of at least 45 and at most 500, especially of at least26 and at most 450, more especially of at least 30 and at most 450, mostespecially of at least 35 and at most 450, for example of at least 40and at most 450, for example of at least 45 and at most 450, for exampleof at least 26 and at most 400, for example of at least 30 and at most400, for example of at least 35 and at most 400, for example of at least40 and at most 400, for example of at least 45 and at most 400, forexample of at least 26 and at most 350, for example of at least 30 andat most 350, for example of at least 35 and at most 350, for example ofat least 40 and at most 350, for example of at least 45 and at most 350,for example of at least 26 and at most 300, for example of at least 30and at most 300, for example of at least 35 and at most 300, for exampleof at least 40 and at most 300, for example of at least 45 and at most300, for example of at least 26 and at most 250, for example of at least30 and at most 250, for example of at least 35 and at most 250, forexample of at least 40 and at most 250, for example of at least 45 andat most 250 mmol/Kg A and B.

Preferably the component C is present in an amount of at most 500, morepreferably at most 450, even more preferably at most 400, mostpreferably at most 350, especially at most 300, more especially at most250 mmol/Kg A and B.

Preferably the peroxydicarbonate-X and the component C are present inany combination of preferred amount or preferred range of amountsdisclosed individually for the peroxydicarboanate-X and the component Cin this section 1.3 in a way that the total amount of C is always atleast equal to or higher than the amount of the peroxydicarbonate-X. Forexample, the peroxydicarbonate-X is present in an amount of at least 26and at most 500 mmol/Kg A and B and the component C is present in anamount of at most 500 mmol/Kg A and B; for example theperoxydicarbonate-X is present in an amount of at least 30 and at most250 mmol/Kg A and B and the component C is present in an amount of atmost 500 mmol/Kg A and B; for example the peroxydicarbonate-X is presentin an amount of at least 30 and at most 250 mmol/Kg A and B and thecomponent C is present in an amount of at most 250 mmol/Kg A and B; forexample the peroxydicarbonate-X is present in an amount of at least 40and at most 500 mmol/Kg A and B and the component C is present in anamount of at most 500 mmol/Kg A and B; for example theperoxydicarbonate-X is present in an amount of at least 40 and at most250 mmol/Kg A and B and the component C is present in an amount of atmost 250 mmol/Kg A and B.

Preferably, the component C of the TPCC of the invention comprisesperoxydicarbonate-X in an amount of at least 5.2, more preferably of atleast 6, even more preferably of at least 7, most preferably of at least8, especially of at least 9, more especially of at least 9.6, even moreespecially of at least 10.4, most especially of at least 12, for exampleof at least 14, for example of at least 16, for example of at least 18,for example of at least 19.2, for example of at least 20, for example ofat least 25, for example of at least 30, for example of at least 40, forexample of at least 50, for example of at least 60, for example of atleast 70, for example of at least 80 for example of at least 90 forexample of at least 95 for example of at least 96, for example of atleast 97, for example of at least 98, for example of at least 99, forexample of at least 99.5, for example at least 99.9 pph of C.Preferably, the TPCC of the invention comprises component C whereincomponent C represents one or more thermal radical initiators, whereineach of the thermal radical initiators is peroxydicarbonate-X as thelatter—and its preferments—are disclosed herein; in other words, theTPCC of the invention does not contain any thermal radical initiatorother than peroxydicarbonate-X as the latter—and its preferments—aredisclosed herein.

If the component C comprises dicetyl peroxydicarbonate in any amountdisclosed herein for any combination of preferred amount or preferredrange of amounts disclosed individually for the peroxydicarboanate-X andthe component C in this section 1.3, then preferably the TPCC may alsocomprise component D as the latter and its preferments are disclosedherein.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.3 can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

1.4 the Component D of the TPCC of the Invention

The terms ‘component D’ and ‘D’ are used herein interchangeably.

The TPCC of the invention may (optionally) further comprise component Dwherein component D represents one or more co-initiators selected fromthe group consisting of onium compounds, sulpho-compounds, and mixturesthereof.

If the TPCC of the invention comprises component D, then preferably thecomponent D is present in an amount of at least 1, more preferably atleast 5, even more preferably at least 10 mmol/Kg A and B. If the TPCCof the invention comprises component D, the preferably the component Dis present in an amount of at most 95 mmol/Kg A and B. If the TPCC ofthe invention comprises component D, then preferably the component D ispresent in an amount of at least 1 and at most 95, more preferably atleast 5 and at most 95, even more preferably at least 10 and at most 95mmol/Kg A and B. These ranges and their preferments apply equally forany co-initiator, any combination of co-initiators as well as for anypreferment thereof, as disclosed herein.

The co-initiator is selected from the group consisting of oniumcompounds, sulpho-compounds, and mixtures thereof. Preferably theco-initiator is selected from the group of onium compounds. Preferablythe co-initiator is selected from the group of sulpho-compounds.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, sulpho-compound-3,and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, andsulpho-compound-3.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-2, and sulpho-compound-3.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, compoundsrepresented by formula VIII-X, and compounds represented by formulaIX-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-3.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, compounds represented by formula VII-X, and compoundsrepresented by formula VIII-X; and wherein the sulpho-compounds areselected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, sulpho-compound-4, andsulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaIV-X, compounds represented by formula V-X, compounds represented byformula VI-X, and compounds represented by formula VII-X; and whereinthe sulpho-compounds are selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4, and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula III-X, compounds represented by formulaV-X, compounds represented by formula VI-X, and compounds represented byformula VII-X; and wherein the sulpho-compounds are selected from thegroup consisting of sulpho-compound-1, sulpho-compound-2,sulpho-compound-3, sulpho-compound-4, and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula V-X, compounds represented by formulaVI-X, and compounds represented by formula VII-X; and wherein thesulpho-compounds are selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula V-X, compounds represented by formulaVI-X; and wherein the sulpho-compounds are selected from the groupconsisting of sulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X,compounds represented by formula V-X; and wherein the sulpho-compoundsare selected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, sulpho-compound-4 andsulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, compounds represented by formula II-X; andwherein the sulpho-compounds are selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3,sulpho-compound-4 and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula II-X; and wherein the sulpho-compounds areselected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, sulpho-compound-4 andsulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula II-X; and wherein the sulpho-compounds areselected from the group consisting of sulpho-compound-1,sulpho-compound-2, sulpho-compound-3, and sulpho-compound-5.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, and compounds represented by formula II-X;and wherein the sulpho-compounds are selected from the group consistingof sulpho-compound-1, sulpho-compound-2, and sulpho-compound-3.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, and compounds represented by formula II-X;and wherein the sulpho-compounds are selected from the group consistingof sulpho-compound-2, and sulpho-compound-3.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X, and compounds represented by formula II-X;and wherein the sulpho-compounds are selected from the group consistingof sulpho-compound-3.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X; and compounds represented by formula II-X.

Preferably the co-initiator is selected from the group consisting ofonium compounds wherein the onium compounds are selected from the groupconsisting of compounds represented by formula II-X.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X and compounds represented by formula II-X andwherein the A⁻ in formulae I-X and II-X is selected from the groupconsisting of halide anions, perhalide anions, phosphate anions,arsenate anions, antimonite anions, sulphonate anions, and borateanions.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X and compounds represented by formula II-X andwherein the A⁻ in formulae I-X and II-X is selected from the group ofhalide anions, perhalide anions, phosphate anions, sulphonate anions,and borate anions.

Preferably the co-initiator is selected from the group consisting ofonium compounds, sulpho-compounds, and mixtures thereof, wherein theonium compounds are selected from the group consisting of compoundsrepresented by formula I-X and compounds represented by formula II-X andwherein the A⁻ in formulae I-X and II-X is selected from the group ofhalide anions.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfinate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate, triethylsulfonium tetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,pentan-3-one O-tosyl oxime, (E)-3,4-dihydronaphthalen-1(2H)-oneO-((4-chlorophenyl)sulfonyl) oxime and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate, triethylsulfonium tetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,(E)-3,4-dihydronaphthalen-1 (2H)-one O-((4-chlorophenyl)sulfonyl) oximeand mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate, triethylsulfonium tetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate, methyl(diphenyl)sulfoniumtetrafluoroborate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-benzylpyridinium hexafluorophosphate, N-ethoxy-2-methylpyridiniumhexafluorophosphate, diethyl(2-oxo-2-phenylethyl)sulfoniumhexafluorophosphate, diphenyl(p-tolyl)sulfonium4-methylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate,tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,N-ethoxy-2-methylpyridinium hexafluorophosphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate, tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate, tri(4-((4-acetylphenyl)thio)phenyl)sulfonium,tetrakis(perfluorophnyl)borate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate, triphenylsulfoniumtrifluoromethanesulfonate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,diphenyl(p-tolyl)sulfonium 4-methylbenzenesulfonate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,diethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone,and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate,2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane,tert-butyl 4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, tert-butyl4-methylbenzenesulfonate, 2-isopropyl-5-methylcyclohexyl4-methylbenzenesulfonate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, tert-butyl4-methylbenzenesulfonate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-dodecylphenyl)iodonium p-toluene sulphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium chloride, bis(4-dodecylphenyl)iodoniumiodide, bis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-dodecylphenyl)iodonium chloride, bis(4-tert-butylphenyl)iodoniumhexafluorophosphate, bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium iodide, bis(4-tert-butylphenyl)iodoniump-toluene sulphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumhexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodoniumchloride, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium p-toluene sulphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium iodide,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,bis(4-tert-butylphenyl)iodonium p-toluene sulphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium p-toluene sulphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium iodide, diphenyliodonium p-toluene sulphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium chloride,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium chloride,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting ofbis(4-tert-butylphenyl)iodonium hexafluorophosphate,(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting of(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate,diphenyliodonium p-toluene sulphate, and mixtures thereof.

Preferably the co-initiator is selected from the group consisting of(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,diphenyliodonium chloride, diphenyliodonium hexafluorphosphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofdiphenyliodonium chloride, diphenyliodonium hexafluorphosphate, andmixtures thereof.

Preferably the co-initiator is selected from the group consisting ofdiphenyliodonium chloride,2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanoneand mixtures thereof.

Preferably the co-initiator is diphenyliodonium chloride.

The onium compounds and their preferments, as well the sulpho-compoundsand their preferments are disclosed in sections 1.4.1 and 1.4.2.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.4 and in sub-sections 1.4.1 and 1.4.2 can be combined witheach other and with any other feature, element, component, embodiment,aspect, range and especially any preferred feature, preferred element,preferred embodiment, preferred aspect, preferred range, preferredcombination of ranges, preferments, embodiments and aspects of theinvention as these are disclosed in the entire application.

1.4.1 the Onium Compound

The onium compound is selected from the group consisting of compoundsrepresented by the following formula Y

Q⁺A⁻  (formula Y)

wherein Q⁺ is a cation selected from the group consisting of cations-B,cations-B1 and cations-B2, as each of them is defined below in i) toiii), respectively:

-   -   i) cations-B: these cations are derived by addition of a hydron        (H⁺) to a mononuclear parent hydride of N, P, As, Sb, Bi, O, S,        Se, Te, Po, F, Cl, Br, I, At (preferably of N, P, O, S, and I,        more preferably of N, S, and I, more preferably of S, and I,        even more preferably of I), and    -   ii) cations-B1: these cations are derivatives of the cations-B,        and are formed by substitution of the cations-B by univalent        groups, and    -   iii) cations-B2: these cations are derivatives of the cations-B,        and are formed by substitution of the cations-B by groups having        two or three free valences on the same atom.        and wherein A⁻ is an anion which is the counter-anion to Q⁺, and        wherein A⁻ is selected from the group consisting of halide        anions, perhalide anions, phosphate anions, arsenate anions,        antimonite anions, sulphonate anions, and borate anions.        Preferably, A⁻ is selected from the group consisting of halide        anions, perhalide anions, phosphate anions, arsenate anions,        sulphonate anions, and borate anions. More preferably, A⁻ is        selected from the group consisting of halide anions, perhalide        anions, phosphate anions, sulphonate anions, and borate anions.        Even more preferably, A⁻ is selected from the group consisting        of halide anions, perhalide anions, phosphate anions, and        sulphonate anions. Most preferably, A⁻ is selected from the        group consisting of halide anions, phosphate anions and        sulphonate anions. Especially A⁻ is selected from the group        consisting of halide anions and sulphonate anions. More        especially A⁻ is selected from the group consisting of halide        anions. Even more especially A⁻ is selected from the group        consisting of of F⁻, Cl⁻, Br⁻, and I⁻. Most especially A⁻ is        selected from the group consisting of Cl⁻, and I⁻. For example        A⁻ is Cl⁻.

Exemplary cations-B include but are not limited to (H₄N⁺) ammonium,(H₃O⁺) oxonium, (H₂F⁺) fluoronium, (H₄P⁺) phosphonium, (H₃S⁺) sulfonium,(H₂Cl⁺) chloronium, (H₄As⁺) arsonium, (H₃Se⁺) selenonium, (H₂Br⁺)bromonium, (H₄Sb⁺) stibonium, (H₃Te⁺) telluronium, (H₂I⁺) iodonium,(H₄Bi⁺) bismuthonium. In the case of cations-B1, the number ofsubstituted hydrogen atoms is, especially in the case of hydrocarbylsubstituents, indicated by the adjectives primary, secondary, tertiaryor quaternary. Exemplary cations-B1 include but are not limited to(Cl₂F⁺) dichlorofluoronium, (CH₃)₂S⁺H dimethylsulfonium (a secondarysulfonium ion), Cl(CH₃)₃P⁺ chlorotrimethylphosphonium, (CH₃CH₂)₄N⁺tetraethylammonium (a quaternary ammonium ion). In the case ofcations-B2 such cations are, where possible, designated by a specificclass name. Exemplary cations-B2 include but are not limited to RC≡O⁺hydrocarbylidyne oxonium ions, R₂C═N⁺H₂X⁻ iminium compounds, RC═NH⁺nitrilium ions.

Exemplary onium compounds comprising a cation-B include but are notlimited to ammonium fluoride, oxonium antimone (V) fluoride, ammoniumtetrafluoroborate. Exemplary onium compounds comprising a cation-B1include but are not limited to benzenediazonium chloride,tetraphenylphosphonium hexafluorphosphate, trimethyloxoniumtetrafluoroborate, triethyloxonium tetrafluoroborate,bis(2,4,6-trimethylpyridine)bromonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate,diphenyliodoniumchloride, diphenyliodonium hexafluorophosphate,diphenyliodonium perchlorate, ethynyl(phenyl)iodonium tetrafluoroborate,triphenylsulfonium hexaflurphosphate. Exemplary onium compoundscomprising a cation-B2 include but are not limited to1-butyl-3-methylimidazolium tetrafluoroborate, N-ethyl acetonitriliumtetrafluoroborate, and N-benzylpyridinium hexafluorophosphate,2,4,6-triphenylpyrylium hydrogensulfate, 2,4,6-trimethylpyryliumtetrafluoroborate, 2,6-di-tert-butyl-4-methylpyryliumtrifluoromethanesulfonate.

Preferably, the onium compound is a compound selected from the groupconsisting of compounds represented by the following formula Y

Q⁺A⁻  (formula Y)

wherein Q⁺ is a cation selected from the group consisting of cations-B1and cations-B2, as each of them is defined below in i) to ii),respectively:

-   -   i) cations-B1: these cations are derivatives of the cations-B,        and are formed by substitution of the cations-B by univalent        groups, and    -   ii) cations-B2: these cations are derivatives of the cations-B,        and are formed by substitution of the cations-B by groups having        two or three free valences on the same atom,        wherein the cations-B are derived by addition of a hydron (H⁺)        to a mononuclear parent hydride of N, P, As, Sb, Bi, O, S, Se,        Te, Po, F, Cl, Br, I, and At (preferably of N, P, O, S, and I,        more preferably of N, S, and I, more preferably of S, and I,        even more preferably of I), and        wherein A⁻ is an anion which is the counter-anion to Q⁺, and        wherein A⁻ is selected from the group consisting of halide        anions, perhalide anions, phosphate anions, arsenate anions,        antimonite anions, sulphonate anions, and borate anions.        Preferably, A⁻ is selected from the group consisting of halide        anions, perhalide anions, phosphate anions, arsenate anions,        sulphonate anions, and borate anions. More preferably, A⁻ is        selected from the group consisting of halide anions, perhalide        anions, phosphate anions, sulphonate anions, and borate anions.        Even more preferably, A⁻ is selected from the group consisting        of halide anions, perhalide anions, phosphate anions, and        sulphonate anions. Most preferably, A⁻ is selected from the        group consisting of halide anions, phosphate anions and        sulphonate anions. Especially A⁻ is selected from the group        consisting of halide anions and sulphonate anions. More        especially A⁻ is selected from the group consisting of halide        anions. Even more especially A⁻ is selected from the group        consisting of of F⁻, Cl⁻, Br⁻, and I⁻. Most especially A⁻ is        selected from the group consisting of Cl⁻, and I⁻. For example        A⁻ is Cl⁻.

Preferably, the onium compound is a compound selected from the groupconsisting of compounds represented by the following formula Y

Q⁺A⁻  (formula Y)

wherein Q⁺ is a cation selected from the group consisting of cations-B1wherein the cations-B1 are derivatives of the cations-B that are formedby substitution of the cations-B by univalent groups, and wherein thecations-B are derived by addition of a hydron (H⁺) to a mononuclearparent hydride of N, P, As, Sb, Bi, O, S, Se, Te, Po, F, Cl, Br, I, andAt (preferably of N, P, O, S, and I, more preferably of N, S, and I,more preferably of S, and I, even more preferably of I), andwherein A⁻ is an anion which is the counter-anion to Q⁺, and wherein A⁻is selected from the group consisting of halide anions, perhalideanions, phosphate anions, arsenate anions, antimonite anions, sulphonateanions, and borate anions. Preferably, A⁻ is selected from the groupconsisting of halide anions, perhalide anions, phosphate anions,arsenate anions, sulphonate anions, and borate anions. More preferably,A⁻ is selected from the group consisting of halide anions, perhalideanions, phosphate anions, sulphonate anions, and borate anions. Evenmore preferably, A⁻ is selected from the group consisting of halideanions, perhalide anions, phosphate anions, and sulphonate anions. Mostpreferably, A⁻ is selected from the group consisting of halide anions,phosphate anions and sulphonate anions. Especially A⁻ is selected fromthe group consisting of halide anions and sulphonate anions. Moreespecially A⁻ is selected from the group consisting of halide anions.Even more especially A⁻ is selected from the group consisting of of F⁻,Cl⁻, Br⁻, and I⁻. Most especially A⁻ is selected from the groupconsisting of Cl⁻, and I⁻. For example A⁻ is Cl⁻.

By the term ‘halide anion’ is meant an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, At⁻. Preferably the halide anion is ananion selected from the group consisting of F⁻, Cl⁻, Br, and I⁻. Morepreferably the halide anion is an anion selected from the groupconsisting of Cl⁻, Br, and I⁻. Even more preferably the halide anion isan anion selected from the group consisting of Cl⁻, and I⁻. Mostpreferably the halide anion is Cl⁻.

By the term ‘perhalide anion’ is meant an anion selected from the groupconsisting of FO₄ ⁻, ClO₄ ⁻, BrO₄ ⁻, IO₄ ⁻. Preferably the perhalideanion is ClO₄ ⁻ (perchlorate anion).

By the term ‘phosphate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula PA

PX⁻  (formula PA)

wherein X is selected from the group consisting of F, Cl, Br, I, At.Preferably the X is selected from the group consisting of F, Cl, Br, andI. More preferably the X is selected from the group consisting of F, Cl,and Br. Even more preferably the X is selected from the group consistingof F, and Cl. Most preferably the X is F. An example of a phosphateanion (and most preferred of the phosphate anions) is PF₆ ⁻.

By the term ‘arsenate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula AA

AsX⁻  (formula AA)

wherein X is selected from the group consisting of F, Cl, Br, I, At.Preferably the X is selected from the group consisting of F, Cl, Br, andI. More preferably the X is selected from the group consisting of F, Cl,and Br. Even more preferably the X is selected from the group consistingof F, and Cl. Most preferably the X is F. An example of an arsenateanion (and most preferred of the arsenate anions) is AsF₆ ⁻.

By the term ‘antimonate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula ATA

SbX⁻  (formula ATA)

wherein X is selected from the group consisting of F, Cl, Br, I, At.Preferably the X is selected from the group consisting of F, Cl, Br, andI. More preferably the X is selected from the group consisting of F, Cl,and Br. Even more preferably the X is selected from the group consistingof F, and Cl. Most preferably the X is F. An example of an antimonateanion (and most preferred of the antimonate anions) is SbF₆ ⁻.

By the term ‘sulphonate anion’ is meant an anion selected from the groupconsisting of anions represented by the following formula SA

wherein R₁″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably aC₇-C₁₂ unsaturated hydrocarbyl, more preferably CH₃C₆H₄. Examples ofsulphonate anions include but are not limited to

Preferably the sulphonate anion is selected from the group consisting of1,1,2,2-tetrafluroethanesulphonate anion, perfluoro-1-butanesulphonateanion and p-toluene sulphate anion. More preferably, the sulphonateanion is p-toluene sulphate anion.By the term ‘borate anion’ is meant an anion selected from the groupconsisting of anions represented by the formula BA, and anionsrepresented by the formula BA-I,

whereinR₂″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆, andR₃″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆, andR₄″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆, andR₅″ is a C₁-C₁₂ optionally substituted hydrocarbyl, preferably a C₁-C₁₂optionally substituted unsaturated hydrocarbyl, more preferably ahalogen substituted aryl, even more preferably is F₅C₆;X is selected from the group consisting of F, Cl, Br, I, At. Preferablythe X is selected from the group consisting of F, Cl, Br, and I. Morepreferably the X is selected from the group consisting of F, Cl, and Br.Even more preferably the X is selected from the group consisting of F,and Cl. Most preferably the X is F.

An example of a borate anion of formula BA (and most preferred of theborate anions of formula BA) is (F₅C₆)₄B⁻[tetrakis(2,3,4,5,6-pentafluorophenyl)borate anion] (see formula below).

An example of a borate anion of formula BA-I (and most preferred of theborate anion of formula BA-I) is BF₄ ⁻. Most preferably the borate anionis an anion selected from the group of anions consisting of (F₅C₆)₄B⁻and BF₄ ⁻.

Preferably the onium compound is selected from the group consisting ofcompounds represented by the following formula I-X, compoundsrepresented by the following formula II-X, compounds represented by thefollowing formula III-X, compounds represented by the following formulaIV-X, compounds represented by the following formula V-X, compoundsrepresented by the following formula VI-X, compounds represented by thefollowing formula VII-X, compounds represented by the following formulaVIII-X, compounds represented by the following formula IX-X,

whereinA⁻ is selected from the group consisting of phosphate anions, sulphonateanions, borate anions and halide anions; andR₁′″ is a C₁-C₁₂ saturated hydrocarbyl, and R₂′″ is a C₁-C₁₂ saturatedhydrocarbyl; andR₃′″ is H or a C₁-C₁₂ hydrocarbyl, and R₄′″ is a C₁-C₁₂ hydrocarbyl; andR₅′″ is H or a C₁-C₁₂ hydrocarbyl, and R₆′″ is a C₁-C₁₂ hydrocarbyl; andR₇′″ is H or a C₁-C₁₂ hydrocarbyl, and R₈′″ is H or a C₁-C₁₂hydrocarbyl; andR₉′″ is H or a C₁-C₁₂ hydrocarbyl, andR₁₀′″ is H or a C₁-C₁₂ hydrocarbyl, and R₁₁′″ is H or a C₁-C₁₂hydrocarbyl, and R₁₂′″ is H or a C₁-C₁₂ hydrocarbyl.

Examples of compounds of formula I-X include but are not limited tobis(4-dodecylphenyl)iodonium hexafluorophosphate,bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and(4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate,the formulae of which are shown below.

Examples of compounds of formula II-X include but are not limited todiphenyliodonium chloride and diphenyliodonium hexafluorphosphate, theformulae of which are shown below.

An example of a compound of formula III-X is N-benzylpyridiniumhexafluorophosphate the formula of which is shown below.

An example of a compound of formula IV-X is N-ethoxy-2-methylpyridiniumhexafluorophosphate the formula of which is shown below.

An example of a compound of formula V-X isdiethyl(2-oxo-2-phenylethyl)sulfonium hexafluorophosphate the formula ofwhich is shown below.

An example of a compound of formula VI-X is diphenyl(p-tolyl)sulfonium4-methylbenzenesulfinate and triphenylsulfoniumtrifluoromethanesulfonate, the formulae of which are shown below.

An example of a compound of formula VII-X istri(4-((4-acetylphenyl)thio)phenyl)sulfoniumtetrakis(perfluorophnyl)borate the formula of which is shown below.

An example of a compound of formula VIII-X is methyl(diphenyl)sulfoniumtetrafluoroborate the formula of which is shown below.

An example of a compound of formula IX-X is triethylsulfoniumtetrafluoroborate the formula of which is shown below.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.4.1 can be combined with each other and with any otherfeature, element, component, embodiment, aspect, range and especiallyany preferred feature, preferred element, preferred embodiment,preferred aspect, preferred range, preferred combination of ranges,preferments, embodiments and aspects of the invention as these aredisclosed in the entire application.

1.4.2 the Sulpho-Compound

The sulpho-compound is selected from the group consisting ofsulpho-compounds-1, sulpho-compounds-2, sulpho-compounds-3,sulpho-compounds-4, sulpho-compounds-5, and mixtures thereof.

By the term ‘sulpho-compound-1’ is meant a compound represented by thefollowing formula L1

wherein R₁′ is a C₁-C₁₀ hydrocarbyl, and R₂′ is a C₁-C₁₀ hydrocarbyl.Examples of a sulpho-compound-1 include but are not limited to2-(((tert-butylsulfonyl)(diazo)methyl)sulfonyl)-2-methylpropane and(diazomethylenedisulfonyl)dicyclohexane.

By the term ‘sulpho-compound-2’ is meant a compound represented by thefollowing formula L2

wherein R₃′ is a C₁-C₁₂ hydrocarbyl, and R₄′ is a C₁-C₁₂ hydrocarbyl.Examples of a sulpho-compound-2 include but are not limited to2-isopropyl-5-methylcyclohexyl 4-methylbenzenesulfonate and cyclohexyl4-methylbenzenesulfonate and cyclohexyl 4-methylbenzenesulfonate.

By the term ‘sulpho-compound-3’ is meant a compound represented by thefollowing formula L3

wherein R₅′ is a C₁-C₁₂ hydrocarbyl, and R₆′ is a C₁-C₁₂ hydrocarbyl andR₇′ is a C₁-C₁₂ saturated hydrocarbyl, and R₈′ is a C₁-C₁₂ saturatedhydrocarbyl. Most preferably, R₅′ is a C₁-C₁₂ hydrocarbyl, and R₆′ is aC₁-C₁₂ hydrocarbyl and R₇′ is CH₃, and R₈′ is CH₃. An example of asulpho-compound-3 is2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone.

By the term ‘sulpho-compound-4’ is meant a compound represented by thefollowing formula L4

wherein R₉′ is a C₁-C₁₂ hydrocarbyl, and R₁₀′ is a C₁-C₁₂ hydrocarbyland R₁₁′ is a C₁-C₁₂ hydrocarbyl. An example of a sulpho-compound-4 ispentan-3-one O-tosyl oxime.

By the term ‘sulpho-compound-5’ is meant a compound represented by thefollowing formula L5

wherein R₁₂′ is a C₁-C₁₂ hydrocarbyl or a substituted hydrocarbyl, andR₁₃′ is a C₁-C₁₂ hydrocarbylene. An example of a sulpho-compound-5 is(E)-3,4-dihydronaphthalen-1(2H)-one O-((4-chlorophenyl)sulfonyl) oxime.

Preferably, the sulpho compound is selected from the group consisting ofsulpho-compound-1, sulpho-compound-2, sulpho-compound-3, andsulpho-compound-5. More preferably, the sulpho compound is selected fromthe group consisting of sulpho-compound-1, sulpho-compound-2, andsulpho-compound-3. Even more preferably, the sulpho compound is selectedfrom the group consisting of sulpho-compound-2, and sulpho-compound-3.Most preferably, the sulpho compound is a sulpho-compound-3. Especially,the sulpho compound is is2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.4.2 can be combined with each other and with any otherfeature, element, component, embodiment, aspect, range and especiallyany preferred feature, preferred element, preferred embodiment,preferred aspect, preferred range, preferred combination of ranges,preferments, embodiments and aspects of the invention as these aredisclosed in the entire application.

1.5 the Component E of the TPCC of the Invention

The terms ‘component E’ and ‘E’ are used herein interchangeably.

The TPCC of the invention may (optionally) further comprise component Ewherein component E represents one or more inhibitors, preferablyselected from the group consisting of phenolic compounds, stableradicals, catechols, phenothiazines, hydroquinones, benzoquinones ormixtures thereof.

If the TPCC of the invention comprises component E, then preferably thecomponent E is present in an amount of at least 5, more preferably atleast 10, even more preferably at least 15, most preferably at least 16,especially at least 18, more especially at least 20, most especially atleast 25, for example at least 30, for example at least 35, for exampleat least 40, for example at least 45 mg/Kg A and B. If the TPCC of theinvention comprises component E, then preferably the component E ispresent in an amount of at most 5000, more preferably at most 4000, evenmore preferably at most 3000, most preferably at most 2500, especiallyat most 2000, more especially at most 1800, most especially at most1500, for example at most 1200, for example at most 1000, for example atmost 900 for example at most 800 for example at most 700 for example atmost 600 for example at most 500, for example at most 400, for exampleis at most 300, for example is at most 260 mg/Kg A and B. Preferably,the amount of component E in the thermosetting powder coatingcomposition of the invention is at least 16 and at most 1500, morepreferably at least 20 and at most 1500, even more preferably at least16 and at most 1000, most preferably at least 20 and at most 1000,especially at least 16 and at most 800, more especially at least 20 andat most 800, most especially at least 16 and at most 600, for example atleast 20 and at most 600, for example at least 25 and at most 800, forexample at least 30 and at most 800, for example at least 40 and at most1500, for example at least 40 and at most 1000, for example at least 40and at most 800, for example at least 40 and at most 700, for example atleast 40 and at most 600, for example at least 40 and at most 500, forexample at least 45 and at most 1500, for example at least 45 and atmost 1000, for example at least 45 and at most 800, for example at least45 and at most 700, for example at least 45 and at most 600, for exampleat least 45 and at most 500, for example at least 45 and at most 300mg/Kg A and B.

An inhibitor may be added either: i) during the preparation of thethermosetting powder coating composition, or ii) during the synthesis ofthe UR, or iii) during the synthesis of the VFUR, or iv) in any one ofi) to iii) in any combination.

Examples of phenolic compounds include 2-methoxyphenol, 4-methoxyphenol,2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol,2,6-di-6-butyl-4-ethyl phenol, 2,4,6-trimethyl-phenol,2,4,6-tris-dimethylaminomethyl phenol,4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-isopropylidene diphenol,2,4-di-t-butylphenol and 6,6′-di-t-butyl-2,2′-methylene di-p-cresol.

Examples of stable radicals include1-oxyl-2,2,6,6-tetramethylpiperidine,1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (a compound also referred toas TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one (a compound alsoreferred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine(a compound also referred to as 4-carboxy-TEMPO),1-oxyl-2,2,5,5-tetramethylpyrrolidine,1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also called3-carboxy-PROXYL and galvinoxyl(2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy).

Examples of catechols include catechol, 4-tert-butylcatechol, and3,5-di-tert-butylcatechol.

Examples of hydroquinones include hydroquinone, 2-methylhydroquinone,2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone,2,6-di-tert-butylhydroquinone, 2,6-dimethylhydroquinone and2,3,5-trimethylhydroquinone.

Examples of benzoquinones include benzoquinone,2,3,5,6-tetrachloro-1,4-benzoquinone, methylbenzoquinone,2,6-dimethylbenzoquinone, and napthoquinone.

Preferably, each of one or more inhibitors is chosen from the groupconsisting of phenolic compounds, stable radicals, catechols,phenothiazines, hydroquinones, benzoquinones or mixtures thereof; morepreferably from the group consisting of phenolic compounds, catechols,phenothiazines, hydroquinones, benzoquinones or mixtures thereof; evenmore preferably from the group consisting of catechols, phenothiazines,hydroquinones, benzoquinones or mixtures thereof; most preferably fromthe group consisting of catechols, hydroquinones, benzoquinones ormixtures thereof; especially from the group consisting of catechols,hydroquinones, benzoquinones or mixtures thereof; more especially fromthe group consisting of catechols, hydroquinones, or mixtures thereof;most especially from the group of hydroquinones.

Preferably, each of one or more inhibitors is chosen from the groupconsisting of hydroquinone, 2-methylhydroquinone,2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone,2,6-di-tert-butylhydroquinone, 2,6-dimethylhydroquinone and2,3,5-trimethylhydroquinone, or mixtures thereof; more preferably fromthe group consisting of hydroquinone, 2-methylhydroquinone,2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone,2,6-di-tert-butylhydroquinone, 2,6-dimethylhydroquinone or mixturesthereof; most preferably from the group consisting of hydroquinone,2-methylhydroquinone, 2-tert-butylhydroquinone,2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, ormixtures thereof; especially from the group of consisting ofhydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone,2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, ormixtures thereof; especially from the group of consisting ofhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone,2,6-di-tert-butylhydroquinone, or mixtures thereof; especially from thegroup of consisting of hydroquinone, 2-tert-butylhydroquinone and2-methylhydroquinone, or mixtures thereof.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.5 can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

1.6 the Component F of the TPCC of the Invention

The terms ‘component F’ and ‘F’ are used herein interchangeably.

The TPCC of the invention may (optionally) further comprise component Fwherein component F represents one or more accelerators selected fromthe group consisting of transition metal compounds, and mixturesthereof.

Preferably the transition metal compounds are selected from the groupconsisting of transition metal salts, and transition metal complexes;more preferably the transition metal compounds are selected from thegroup consisting of transition metal organic salts, and transition metalcomplexes; most preferably the transition metal compounds are selectedfrom the group consisting of transition metal organic acid salts, andderivatives of transition metal organic acid salts. Examples of suitabletransition metal compounds are transition metal carboxylates, transitionmetal acetoacetates, for example transition metal ethylhexanoate.Preferably the transition metal compounds are selected from the groupconsisting of transition metal compounds and transition metal complexesof the following transition metals Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,Zn, Mo, and W; more preferably Mn, Fe, Co, and Cu, even more preferably,Mn, Fe, and Cu. Preferably the transition metal compounds are selectedfrom the group consisting of transition metal organic salts andtransition metal complexes of the following transition metals Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and W; more preferably Mn, Fe, Co, andCu, even more preferably, Mn, Fe, and Cu. Preferably the transitionmetal compounds are selected from the group consisting of transitionmetal organic acid salts, and derivatives of transition metal organicacid salts of the following transition metals Sc, Ti, V, Cr, Mn, Fe, Co,Ni, Cu, Zn, Mo, and W; more preferably Mn, Fe, Co, and Cu, even morepreferably, Mn, Fe, and Cu. Preferably the transition metal compoundsare selected from the group consisting of transition metal carboxylates,and transition metal acetoacetates of the following transition metalsSc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and W; more preferably Mn,Fe, Co, and Cu, even more preferably, Mn, Fe, and Cu. If a coppercompound is used, it may for example be in the form of a Cu⁺ salt or aCu²⁺ salt. If a manganese compound is used, it may for example be in theform of a Mn²⁺ salt or a Mn³⁺ salt. If a cobalt compound is used, it mayfor example be in the form of a Co²⁺ salt or a Co³⁺ salt. If an ironcompound is used, it may for example be in the form of a Fe²⁺ salt or aFe³⁺ salt. Examples of transition metal compounds include but are notlimited to Cu⁺ salts, Cu²⁺ salts, Mn²⁺ salts, Mn³⁺ salts, Co²⁺ salts,Co³⁺ salts, Fe²⁺ salts and Fe³⁺ salts.

If the TPCC of the invention comprises component F, then preferably thecomponent F is present in an amount of at least 0.000003 and at most 50,more preferably in an amount of at least 0.00003 and at most 45, evenmore preferably in an amount of at least 0.0003 and at most 40, mostpreferably in an amount of at least 0.003 and at most 35, especially inan amount of at least 0.03 and at most 30, more especially of at least0.1 and at most 20, even more especially in an amount of at least 0.2and at most 18, most especially in an amount of at least 0.3 and at most15, for example in an amount of at least 0.5 and at most 12, for examplein an amount of at least 1 and at most 10 mg/Kg A and B.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.6 can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

1.7 Other Components of the TPCC of the Invention

The thermosetting powder coating composition of the invention may(optionally) further comprise waxes, pigments, fillers, degassingagents, flow agents, appearance enhancing agents, photoinitiators,stabilizers such as light stabilizers. The pigments may be inorganic ororganic. Suitable inorganic pigments include for example, titaniumdioxide, zinc sulphide, zinc phosphate, mica, iron oxide and/or chromiumoxide. Suitable organic pigments include for example quinacridones,phthalocyanines, perylenes, pyrroles. Suitable fillers include forexample metal oxides, silicates, carbonates and sulphates. Suitablestabilizers include for example primary and/or secondary antioxidantsand UV stabilizers for example quinones, (sterically hindered) phenoliccompounds, phosphonites, phosphites, thioethers and HALS (hindered aminelight stabilizers). Examples of suitable degassing agents includecyclohexane dimethanol bisbenzoate, benzoin and benzoin derivatives suchas for example those described in WO02/50194, the relevant passages ofwhich are incorporated herein by reference. Examples of flow agentsinclude Byk® 361 N and Resiflow® PV-5.

The thermosetting powder coating composition of the invention can becured via heat (heat-curable thermosetting powder coating composition)and/or radiation (radiation curable thermosetting powder coatingcomposition). Preferably, the thermosetting powder coating compositionof the invention is heat-curable without being necessary to useradiation for curing. Heat curing has the advantage that it does notrequire the use of additional and rather expensive equipment, forinstance equipment that generates UV light or accelerated electrons andin only one step involving heating of the thermosetting powder coatingcomposition the latter is melted and cured onto a substrate. In contrastto that, a thermosetting powder coating composition that requiresradiation curing, the curing of said composition requires two steps, oneto melt (heating step) and one to cure (radiation cure typically inducedvia UV light or electron beam irradiation) the composition. Heat curingis especially desirable for coating 3D objects.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 1.7 and their sub-sections, can be combined with each other andwith any other feature, element, component, embodiment, aspect, rangeand especially any preferred feature, preferred element, preferredembodiment, preferred aspect, preferred range, preferred combination ofranges, preferments, embodiments and aspects of the invention as theseare disclosed in the entire application.

2. Process for Making the Thermosetting Powder Coating Compositions ofthe Invention

The thermosetting powder coating compositions of the invention may beprepared by mixing the separately weighed-out components in a premixer,heat the obtained premix, for example in a kneader, preferably in anextruder to obtain an extrudate, cool down the obtained extrudate untilit solidifies and grind it into granules or flakes that are furtherground to reduce the particle size followed by appropriateclassification to obtain a powder coating composition of the rightparticle size.

Alternatively, the thermosetting powder coating compositions of theinvention may be prepared by mixing the separately weighed-out componentB with the component A in a premixer, heat the obtained premix, forexample in a kneader, preferably in an extruder to obtain an extrudate,cool down the obtained extrudate until it solidifies and grind it intogranules or flakes that are further ground to reduce the particle size.Subsequently, mixing the rest of the separately weighed-out componentsand the extrudate of components A and B, in a premixer, heat theobtained premix, for example in a kneader, preferably in an extruder toobtain an extrudate, cool down the obtained extrudate until itsolidifies and grind it into granules or flakes that are further groundto reduce the particle size followed by appropriate classification toobtain a powder coating composition of the right particle size.

Preferably, the thermosetting powder coating composition of theinvention is prepared by a process comprising the steps of:

-   -   a. mixing the components of the thermosetting powder coating        composition according to the invention to obtain a premix;    -   b. heating the premix preferably in an extruder, preferably up        to and including the decomposition temperature of the component        C, more preferably up to and including 85° C., to obtain an        extrudate;    -   c. cooling down the extrudate to obtain a solidified extrudate;        and    -   d. grinding the solidified extrudate into smaller particles to        obtain the thermosetting powder coating composition.

Preferably, the thermosetting powder coating composition of theinvention is prepared by a process comprising the steps of:

-   -   a. mixing the components A and B to obtain a premix 1;    -   b. heating the premix 1, preferably in an extruder, to obtain an        extrudate of components A and B, namely extrudate 1;    -   c. cooling down the extrudate 1 to obtain a solidified extrudate        1; and    -   d. grinding the solidified extrudate 1 into smaller particles to        obtain a mixture of components A and B, namely mixture 1; and    -   e. mixing the rest of the components of the thermosetting powder        coating composition of the invention with the mixture 1, to        obtain a premix 2;    -   f. heating the premix 2, preferably in an extruder, preferably        up to and including the decomposition temperature of the        component C, more preferably up to and including 85° C., to        obtain an extrudate 2;    -   g. cooling down the extrudate 2 to obtain a solidified extrudate        2; and    -   h. grinding the solidified extrudate 2 into smaller particles to        obtain the thermosetting powder coating composition.

Preferably, the thermosetting powder coating composition of theinvention is prepared by a process comprising the steps of:

-   -   a. mixing the components A and B to obtain a premix 1;    -   b. heating the premix 1, preferably in an extruder, to obtain an        extrudate of components A and B, namely extrudate 1;    -   c. cooling down the extrudate 1 to obtain a solidified extrudate        1; and    -   d. grinding the solidified extrudate 1 into smaller particles to        obtain a mixture of components A and B, namely mixture 1; and    -   e. mixing the rest of the components of the thermosetting powder        coating composition of the invention with the mixture 1, to        obtain a premix 2;    -   f. heating the premix 2, preferably in an extruder, preferably        up to and including the decomposition temperature of the        component C, more preferably up to and including 85° C., to        obtain an extrudate 2;    -   g. cooling down the extrudate 2 at a temperature of at most 75,        preferably of at most 50° C. for at least 30 minutes, preferably        for at least 60 minutes, more preferably for at least 90        minutes, even more preferably for at least 120 minutes, to        obtain a solidified extrudate 2; and    -   h. grinding the solidified extrudate 2 into smaller particles to        obtain the thermosetting powder coating composition.

Preferably, the premix 1 is heated to a temperature at least 5, morepreferably at least 10° C. below the temperature at which it is intendedto cure the thermosetting powder coating composition.

Preferably the thermosetting powder coating composition of the inventionis a one component (1K) system or equally a one component thermosettingpowder coating composition. With a ‘one component system’, also called a1K system, is meant that all the components of the thermosetting powdercoating composition form part of one powder. In contrast to that, a ‘twocomponent system’, also called 2K system, is a thermosetting powdercoating composition which is composed of at least two different powderswith different chemical compositions, wherein said system keeps thereactive components physically separated. The compositions of the atleast two different powders in the 2K system are usually selected suchthat each powder contains a component which is needed for curing but isabsent from the other powder(s). This separation allows preparation ofthe individual powder composition in a heated state (such as by meltmixing) without the initiation of the cure reaction.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 2 can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

3. Processes for Coating an Article with the Thermosetting PowderCoating Composition of the Invention

In another aspect, the invention relates to a process for coating asubstrate comprising the steps of:

-   -   a. applying the thermosetting powder coating composition of the        invention to an article as said article is defined herein;    -   b. heating and/or radiating the thermosetting powder coating        composition for enough time (curing time) and at a suitable        temperature to cure (curing temperature) the thermosetting        powder coating composition to obtain the coated article.

The composition of the invention may be applied using the techniquesknown to the person skilled in the art, for example using electrostaticspray or electrostatic fluidized bed or flame spray.

Heating of the coated substrate may be done using conventional methods,such as with an infrared (IR) oven, convection oven and/or with an (N)IRlamp. Even microwave equipment may be used to heat the substrate.

The TPCC of the invention may be cured at a temperature ranging from 85to 225° C. for a time that may range from 3 up to 60 minutes.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 3 can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

4. Other Aspects and Embodiments of the Invention

In another aspect the invention provides for a process for making acured thermosetting powder coating composition comprising the step ofcuring the thermosetting powder coating composition of the invention.

In another aspect, the invention provides for a cured thermosettingpowder coating composition obtained by curing of the thermosettingpowder coating composition of the invention; preferably the curedthermosetting powder coating composition is obtainable by the processfor making the cured thermosetting powder coating composition. Forexample, the cured thermosetting powder coating composition may bederived or is obtainable by a 3D-printing process.

In another aspect, the invention relates to an article of any shape,size or form, for example a substrate, having coated and cured thereon athermosetting powder coating composition as defined herein. Preferably,said article is selected from the group consisting of heat-sensitivearticles and non-heat sensitive articles; more preferably said articleis selected from the group consisting of wood for example low densityfibre board, medium density fibreboard and high density fibreboard,plastic, thermoplastic composite, thermoset composite, fibre reinforcedcomposites, sandwich materials e.g. sandwich materials comprising heatsensitive foam core, metal and combinations thereof.

Heat-sensitive articles for example heat-sensitive substrates, includeplastic articles, wood articles for example solid wood, such as forexample: hard wood, soft wood, plywood; veneer, particle board, lowdensity fibre board, medium density fibreboard and high densityfibreboard, OSB (Oriented Strand Board) wood laminates, chipboard andother articles in which wood is an important constituent, such as forexample foil covered wooden articles, engineered wood, plastic modifiedwood, plastic articles or wood plastic compounds (WPC); articles withcellulosic fibres, for example cardboard or paper articles; textile andleather articles. Examples of plastic articles include unsaturatedpolyester resinbased compositions, ABS (acrylonitril butadiene styrene),melamine-formaldehyde resins, polycarbonate, polyethylene,polypropylene, ethylene-propylene-diene monomer (EPDM), thermoplasticolefin (TPO), polyurethane (PU), polypropylene oxide (PPO), polyethyleneoxide (PEO), polyethyleneterephthalate and nylon, for example polyamide6,6 and mixtures thereof, for example polycarbonate-ABS. Otherheat-sensitive articles include objects that are a combination of anon-heat-sensitive part such as metal parts with a heat-sensitive part,such as any one of the aforementioned for example plastic hosing withheavy metal parts, strips for example aluminium frames with heat stripsetc.

Specific wood coating markets where the thermosetting powder coatingcompositions of the invention may be used include domestic furniture,such as tables, chairs, cabinets, etc., bedroom and bathroom furniture,office furniture, contract furniture such as school and child furniture,hospital furniture, restaurant and hotel furniture, kitchen cabinets andfurniture, (flat) panels for interior design, interior and exteriorwindows and doors, interior and exterior window frames and door frames,exterior and interior sidings and wooden flooring.

Specific plastic coating markets where thermosetting powder coatingcompositions of the invention may be used include automotiveapplications, such as interior car parts, wheel covers, bumpers, underthe hood parts etc., flexible flooring, sporting goods, cosmetics,audio-visual applications, such as TV sets, computer housing, phones,etc., household appliances and satellite dishes.

Typical examples of non-heat-sensitive articles include glass, ceramic,composite, fibre cement board, or metal, for example aluminum, copper orsteel articles, for instance carbon steel, where the main alloyingconstituent is carbon. Carbon steel usually contains carbon 0.2 and 1.5%w/w based on the total alloy composition and often contains otherconstituents such as manganese, chromium, nickel, molybdenum, copper,tungsten, cobalt, or silicon, depending on the desired steel properties.Steel has properties similar to iron if the amount of carbon is not toohigh, for example not more than 1.5% w/w based on the total alloycomposition. The steel may be surface treated (treatment with zinc, orzinc phosphate or iron phosphate etc.) or non-surface treated.

In another aspect, the invention relates to a powder coating obtained bypartial or full cure of the thermosetting powder coating composition ofthe invention. The powder coating can be a primer, top coat or anintermediate coating.

In another aspect, the invention relates to the use of any one of thecompositions according to the invention to fully or partially coat anarticle.

In another embodiment the invention relates to the use of any one of thecompositions of the invention to coat a heat-sensitive articlepreferably wood for example low density fibre board, medium densityfibreboard and high density fibreboard, plastic, etc., or combinationsthereof.

In another aspect, the invention relates to an article that is fully orpartially coated with any one of the compositions of the invention.

In one embodiment of the invention the substrate is a non-heat-sensitivesubstrate, for example glass, ceramic, fibre cement board, or metal, forexample aluminum, copper or steel, preferably metal.

In yet another embodiment, the invention provides for a use of thecomposition of the invention to coat a heat-sensitive article as definedherein and/or a non-heat-sensitive article as defined herein.

In yet another embodiment, the invention provides for a use of thethermosetting powder coating compositions of the invention to coat anarticle wherein the article is a heat-sensitive article for example woodsuch as low density fibre board, medium density fibreboard and highdensity fibreboard, plastic and combinations thereof.

In yet another embodiment, the invention provides for a use of thethermosetting powder coating compositions of the invention to coat anarticle wherein the article is a non-heat-sensitive article for exampleglass, ceramic, composite, fibre cement board, or metal, for examplealuminum, copper or steel articles, for instance carbon steel.

In yet another embodiment, the invention provides for a use of thethermosetting powder coating compositions of the invention to coat anarticle wherein the article is a heat-sensitive article for example woodsuch as low density fibre board, medium density fibreboard and highdensity fibreboard, plastic and combinations thereof and also to coat anarticle wherein the article is a non-heat-sensitive article for exampleglass, ceramic, composite, fibre cement board, or metal, for examplealuminum, copper or steel articles, for instance carbon steel.

In another aspect of the invention there is provided a use of:

-   -   a thermosetting powder coating composition as disclosed herein;        or    -   a cured thermosetting powder coating composition as disclosed        herein; or    -   an article having coated thereon a thermosetting powder coating        composition as the latter is disclosed herein, or    -   an article having coated and cured thereon a thermosetting        powder coating composition as the latter is disclosed herein, in        powder coatings, powder coatings for heat-sensitive articles,        powder coatings for non-heat-sensitive articles, 3D-printing,        automotive applications (car parts, agricultural machines,        composite structures, ceramic structures, etc.), marine        applications (ships, boats), aerospace applications (planes,        helicopters, composite structures, ceramic structures, etc.),        medical applications (artificial joints, meshes, woven or        non-woven sheets, tapes, ribbons, bands, cables, tube-like        products for e.g. ligament replacement, composite structures,        ceramic structures, etc.), defense applications (ballistic        protection, body armor, ballistic vests, ballistic helmets,        ballistic vehicle protection, composite structures, ceramic        structures, etc.), sports/recreational applications (fencing,        skates, skateboarding, snowboarding, suspension lines on sport        parachutes, paragliders, kites, kite lines for kite sports,        climbing equipment, composite structures, ceramic structures,        etc.), architectural applications (windows, doors,        (pseudo-)walls, cables, etc.), bottling applications, household        applications (household appliances, whitegoods, furniture,        computer housings, etc.), machinery applications (can and bottle        handling machine parts, moving parts on weaving machines,        bearings, gears, composite structures, ceramic structures,        computer housings, etc.), can applications, coil applications,        energy applications for e.g. generators for wind, tide or solar        energy, textile applications for e.g. fabrics, this can be very        broad from impregnation technical textiles to for example        complete composites both as coating and as a binder for        composites, and electrical applications for e.g. cabinets for        electrical wire or switch boards.

In another aspect of the invention there is provided a process formaking either powder coatings, or powder coatings for heat-sensitivearticles, or powder coatings for non-heat-sensitive articles, orcompositions suitable for 3D-printing, or compositions suitable forapplications selected from the group consisting of automotiveapplications, marine applications, aerospace applications, medicalapplications, defense applications, sports/recreational applications,architectural applications, bottling applications, householdapplications, machinery applications, can applications, coilapplications, energy applications, textile applications and electricalapplications, or articles suitable for applications selected from thegroup consisting of automotive applications, marine applications,aerospace applications, medical applications, defense applications,sports/recreational applications, architectural applications, bottlingapplications, household applications, machinery applications, canapplications, coil applications, energy applications, textileapplications and electrical applications, wherein at least one of thefollowing i) to iv), is used

-   -   i) a thermosetting powder coating composition as disclosed        herein,    -   ii) a cured thermosetting powder coating composition as        disclosed herein,    -   iii) an article having coated thereon a thermosetting powder        coating composition as the latter is disclosed herein,    -   iv) an article having coated and cured thereon a thermosetting        powder coating composition as the latter is disclosed herein.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure disclosed in thissection 5, can be combined with each other and with any other feature,element, component, embodiment, aspect, range and especially anypreferred feature, preferred element, preferred embodiment, preferredaspect, preferred range, preferred combination of ranges, preferments,embodiments and aspects of the invention as these are disclosed in theentire application.

Yet, another aspect of the invention is a thermosetting powder coatingcomposition selected from the group consisting of thermosetting powdercoating compositions according to InvPCC1-InvPCC31.

Yet, another aspect of the invention is a powder coating selected fromthe group consisting of powder coatings according to InvPC1-InvPC31.

Many other variations and embodiments of the invention will be apparentto those skilled in the art and such variations are contemplated withinthe scope of the claimed invention.

Unless otherwise explicitly stated, any feature, element, component,embodiment, aspect, range and especially any preferred feature,preferred element, preferred embodiment, preferred aspect, preferredrange, preferred combination of ranges, preferments, embodiments andaspects in connection with any piece of disclosure concerning theinvention and disclosed in the entire application can be combined witheach other and with any other feature, element, component, embodiment,aspect, range and especially any preferred feature, preferred element,preferred embodiment, preferred aspect, preferred range, preferredcombination of ranges, preferments, embodiments and aspects of theinvention as these are disclosed in the entire application.

Further aspects of the invention and preferred features thereof aregiven in the claims herein.

The invention will now be described in detail with reference to thefollowing non limiting examples which are by way of illustration only.

EXAMPLES

The invention is explained in more detail with reference to thefollowing non-limiting examples.

In the Examples section, the abbreviation UR represents unsaturatedresin comprising ethylenic unsaturations, the abbreviation VU representsvinyl urethanes, the abbreviation VFUR represents vinyl functionalizedurethane resins used as curing agents, the abbreviation PCC representsthermosetting powder coating composition and the abbreviation PCrepresents powder coating. In all the examples the unsaturated resinscomprising ethylenic unsaturations (UR) were unsaturated polyesterresins comprising 2-butenedioic acid ethylenic unsaturations.

All powder coating compositions presented in the Examples werethermosetting powder coating compositions (TPCC).

In the Examples section the abbreviation ‘Comp’ denotes a ComparativeExample of either a thermosetting powder coating composition e.g.CompPCC1, or a powder coating e.g. CompPC1. In the Examples section theabbreviation ‘Inv’ denotes an Inventive Example of a thermosettingpowder coating composition e.g. InvPCC1, or a powder coating e.g.InvPC1.

In this section (Examples), any method for the measurement of aparameter for a UR is meant to equally apply for any acrylic resin,polyurethane, epoxy resin, polyamide, polyesteramide, polycarbonate,polyurea and polyester resin e.g. for an unsaturated polyester resin,for an unsaturated polyester resin comprising ethylenic unsaturationssuch as an acrylated polyester resin, unsaturated polyester resincomprising di-acid ethylenic unsaturations, for an unsaturated polyesterresin comprising 2-butenedioic acid ethylenic unsaturations, that a URmay be selected from.

In this section (Examples), any method for the measurement of aparameter for a VU is meant to equally apply for any VU such as anycrystalline VU-c e.g. any crystalline VEU-c, any crystalline VESU-c, anycrystalline VEESU-c.

In this section (Examples), any method for the measurement of aparameter for a VFUR is meant to equally apply for any VFUR such as anycrystalline VFUR-c e.g. such as any crystalline VEFUR-c e.g. anycrystalline VESFUR-c, any crystalline VEESFUR-c.

Any reference to paragraph numbers mentioned in the Examples section,refers to paragraphs mentioned in the Examples section.

1. Chemicals, Raw Materials; Analytical Methods and Techniques 1.1Chemicals & Raw Materials

Perkadox® 24-FL (supplied by AkzoNobel Polymer Chemicals), is a solidmixture of dicetyl peroxydicarbonate (peroxydicarbonate-X) and waterwherein the amount of dicetyl peroxydicarbonate is 94.5% w/w on thesolid mixture; water is the carrier material for the dicetylperoxydicarbonate.

Perkadox® 26 (supplied by AkzoNobel Polymer Chemicals), is a solidmixture of dimyristyl peroxydicarbonate (peroxydicarbonate-X) and waterwherein the amount of dimyristyl peroxydicarbonate is 94.5% w/w on thesolid mixture; water is the carrier material for the dimyristylperoxydicarbonate.

Perkadox® 16 (supplied by AkzoNobel Polymer Chemicals), is a solidmixture of di(4-tert-butylcyclohexyl) peroxydicarbonate(peroxydicarbonate-X) and water wherein the amount ofdi(4-tert-butylcyclohexyl) peroxydicarbonate is 95.5% w/w on the solidmixture; water is the carrier material for thedi(4-tert-butylcyclohexyl) peroxydicarbonate.

Laurox®-S(supplied by AkzoNobel Polymer Chemicals), is a solid mixtureof dilauroyl peroxide (peranhydride) and water wherein the amount ofdilauroyl peroxide is 99% w/w on the solid mixture; water is the carriermaterial for the dilauroyl peroxide.

Perkadox® PM-W75 (supplied by AkzoNobel Polymer Chemicals), is a solidmixture of bis(4-methylbenzoyl) peroxide (peranhydride) and waterwherein the amount of bis(4-methylbenzoyl) peroxide is 75% w/w on thesolid mixture; water is the carrier material for bis(4-methylbenzoyl)peroxide.

Trigonox® C-50D PD (supplied by AkzoNobel Polymer Chemicals) is a solidmixture of t-butyl peroxybenzoate (perester) and silicium oxide whereinthe amount of t-butyl peroxybenzoate is 50% w/w on the solid mixture;silicium oxide is the carrier material for the t-butyl peroxybenzoate.

Trigonox® EHP (supplied by AkzoNobel Polymer Chemicals), is a liquidmixture of di(2-ethylhexyl) peroxydicarbonate (peroxydicarbonate) andwater wherein the amount od di(2-ethylhexyl) peroxydicarbonate is 98%w/w on the liquid mixture; water is the carrier material fordi(2-ethylhexyl) peroxydicarbonateperoxydicarbonate. Trigonox® EHP is aperoxydicarbobate.

Trigonox® 23 (supplied by AkzoNobel Polymer Chemicals), is a liquidmixture of tert-butyl peroxyneodecanoate (perester) and water whereinthe amount tert-Butyl peroxyneodecanoate is 95% w/w on the liquidmixture; water is the carrier material tert-Butyl peroxyneodecanoate.Trigonox® 23 is a perester.

Trigonox® 423 C70 (supplied by AkzoNobel Polymer Chemicals), is a liquidmixture of 1,1,3,3-tetramethylbutyl peroxyneodecanoate (perester) andOMS (=odorless mineral spirits), wherein the amounttert-1,1,3,3-tetramethylbutyl peroxyneodecanoate is 70% w/w on theliquid mixture; water is the carrier material 1,1,3,3-tetramethylbutylperoxyneodecanoate.

Cobalt stearate (solid, purity of 98%) (supplied by Alfa Aesar) was useda transition metal compound.

Kronos® 2360 (supplied by Kronos Titan GmbH) is titanium dioxide and wasused as a white pigment.

t-Butyl hydroquinone (supplied by Sigma-Aldrich) was used as aninhibitor.

Resiflow® PV-5 (supplied by Worlee-Chemie GmbH) was used as a flowcontrol agent.

Diphenyliodonium chloride (supplied by Sigma-Aldrich) is an oniumcompound and it reads on formula II-X.

Diethylene glycol monovinylether (liquid; purity 99%) was supplied byBASF.

Triethylene glycol monovinylether (liquid; purity 99%) was supplied byBASF. 4-hydroxybutyl vinylether (liquid; purity 99%) was supplied byBASF.

Any other chemicals mentioned in the Examples and not explicitlymentioned in this paragraph, were supplied by Aldrich and they were usedas supplied.

1.2 Analytical Methods and Techniques

The methods described 1.2.1-1.2.6 for the measurement of propertiesdisclosed herein for a UR applies analogously for any UR that may formpart of component A as disclosed in the entire application, e.g. acrylicresin, polyurethane, epoxy resin, polyamide, polyesteramide,polycarbonate, polyurea and polyester resin e.g. for an unsaturatedpolyester resin, for an unsaturated polyester resin comprising ethylenicunsaturations such as an acrylated polyester resin, unsaturatedpolyester resin comprising di-acid ethylenic unsaturations, for anunsaturated polyester resin comprising 2-butenedioic acid ethylenicunsaturations.

The methods described 1.2.1-1.2.6 for the measurement of propertiesdisclosed herein for a VFUR applies analogously for any VFUR that mayform part of component B as disclosed in the entire application, e.g. acrystalline VFUR-c such as a crystalline VEFUR-c, a crystallineVESFUR-c, a crystalline VEESFUR-c.

The methods described 1.2.1-1.2.6 for the measurement of propertiesdisclosed herein for a VU applies analogously for any VU that may formpart of the component B as disclosed in the entire application, e.g. acrystalline VU-c such as a crystalline VEU-c, a crystalline VESU-c, acrystalline VEESU-c.

The methods described 1.2.6, 1.2.8 and 1.2.9 for the measurement ofproperties disclosed herein for a TPCC of the invention appliesanalogously for any TPCC of the invention as disclosed in the entireapplication.

1.2.1 Method for Measuring the Number Average Molecular Weight (M_(n))(Herein Abbreviated as ‘GPC Method’)

The number average molecular weight (M_(n)) was measured via GelPermeation Chromatography (GPC) calibrated with a set of polystyrenestandards (type EASICAL PS1 and 2 from Agilent) with a molecular weightrange of from 500 up to 2.5×10⁶ g/mol and using as eluent a mixture oftetrahydrofuran (THF) 99.92% and 0.08% acetic acid, at a flow rate of 1mL eluent/minute at 40° C. More specifically, 40 mg of a sample of forexample UR or VU or VFUR—as the case may be—, were dissolved in 700 μLNMP (N-methyl-pyrrolidone) for 20 minutes at 100° C. The solution thusproduced was subsequently cooled down to 25° C., and 5 mL of eluent wereadded to the solution. 40 μL of the solution thus prepared were injectedinto the pre-column (as this is described below) for the GPC measurementto be carried out. The GPC measurements were carried out on a WatersAlliance HPLC system equipped with: i) a Waters Alliance 2414 refractiveindex detector at 40° C., and ii) a Waters Alliance 2695 separationmodule equipped with a pre-column of mixed-C type, PLgel 5 μm Guard,50×7.5 mm (PL1110-1520 from Agilent) and two consecutive PL-gel columnsof Mixed-C type with I/d=300/7.5 mm (PL1110-6500 from Agilent), andfilled with particles having a particle size of 5 μm (supplied by thePolymer Laboratories) and c) software for analyzing the obtainedchromatograph and measuring the M_(n).

1.2.2 Method for Measuring the Melt Viscosity

Melt viscosity (herein mentioned as viscosity, in Pa·s) measurementswere carried out at 160° C. on a Brookfield CAP 2000+H Viscometer. Theapplied shear-rate was 70 s⁻¹ and a 19.05 mm spindle (cone spindleCAP-S-05 (19.05 mm, 1.8°) was used.

1.2.3 Method for Measuring the Acid Value (AV)

The acid value (AV) was measured according to ISO 2114. The AV is givenas the mass of potassium hydroxide (KOH) in milligrams that is requiredto neutralize one gram of the tested substance and is used as a measureof the concentration of carboxylic acid groups present.

1.2.4 Method for Measuring the Hydroxyl Value (OHV)

The hydroxyl value (OHV) was measured according to ISO 4629. The OHV isgiven as the mass of potassium hydroxide (KOH) in milligrams that isrequired to neutralize one gram of the tested substance and is used as ameasure of the concentration of hydroxyl groups present.

1.2.5 Method for Measuring the WPU (Herein Abbreviated as ‘¹H-NMR MethodWPU’)

The WPU was measured via ¹H-NMR spectroscopy according to the methodentitled—for simplicity—‘¹H-NMR method WPU’ which is presented herein.The estimated margin of error of this method for determining the WPU is+/−2%; the margin of error was determined on the basis of measuringthree samples of the same lot of a UR or a VFUR or a VU.

More specifically, said WPU was measured via ¹H-NMR spectroscopy asexplained herein after and it was calculated according to the followingequation EX2:

$\begin{matrix}{{WPU} = \left\lbrack {\frac{W_{pyr}}{W_{resin}}\frac{1}{{MW}_{pyr}}\frac{A_{c = c}/N_{c = c}}{A_{pyr}/N_{pyr}}} \right\rbrack^{- 1}} & ({EX2})\end{matrix}$

wherein,W_(pyr) is the weight of pyrazine (internal standard),W_(resin) is the weight of UR such as an unsaturated polyester resincomprising 2-butenedioic acid ethylenic unsaturations, or the weight ofa curing agent such as a VFUR or a VU; W_(pyr) and W_(resin) areexpressed in the same units.MW_(pyr) is the molecular weight of the pyrazine (=80 Da) (internalstandard).A_(pyr) is the peak area for methine protons attached to the aromaticring of pyrazine and N_(pyr) is the number of the methine protons ofpyrazine (=4).

In case of a UR:

A_(C═C) is the peak area for methine protons ( . . . —CH═ . . . ) of theethylenic unsaturations (>C═C<) of the UR; N_(C═C) is the number ofmethine protons ( . . . —CH═ . . . ) attached to the ethylenicunsaturations (≥C═C<) of the UR.

In case of a VFUR or a VU—as the case may be—:

A_(C═C) is the peak area for the methine proton ( . . . —CH═ . . . ) ofthe vinyl groups ( . . . —CH═CH₂) in the VFUR or in the VU—as the casemay be—; N_(C═C) is the number of methine protons ( . . . —CH═ . . . )of the vinyl groups ( . . . —CH═CH₂) in the VFUR or in the VU—as thecase may be—.

The peak areas of the methine protons of pyrazine and methine protons (. . . —CH═ . . . ) of the ethylenic unsaturations (≥C═C<) of the UR inEX2 were measured as follows: A sample of 75 mg of UR was diluted at 25°C. in 1 ml deuterated chloroform containing a known amount (mg) ofpyrazine as internal standard for performing ¹H-NMR spectroscopy.Subsequently, the ¹H-NMR spectrum of the UR sample was recorded at 25°C. on a 400 MHz BRUKER NMR-spectrometer. Afterwards, the chemical shifts(ppm) of the methine protons of pyrazine and the methine protons ( . . .—CH═ . . . ) of the ethylenic unsaturations (<C═C<) of the UR wereidentified; the chemical shifts (ppm) of the methine protons of pyrazineand the methine protons ( . . . —CH═ . . . ) of the ethylenicunsaturations (<C═C<) of the UR in EX2 measured on a 400 MHz BRUKERNMR-spectrometer in methanol and deuterated chloroform were at about 8.6and at about 6.4-6.9 ppm, respectively. Subsequently, with the help ofsuitable commercially available software for analyzing ¹H-NMR spectrasuch as ACD/Spectrus Processor software provided by ACD/Labs, the peakareas of the methine protons of pyrazine and methine protons ( . . .—CH═ . . . ) of the ethylenic unsaturations (<C═C<) of the UR of EX2were measured and from these values the WPU was determined according toEX2.

If 75 mg of a UR is not soluble at 25° C. in 1 ml of deuteratedchloroform, then any other suitable solvent or mixture of solvents knownto the skilled person for performing the ¹H-NMR spectroscopy may beused; for example DMSO (dimethyl sulfoxide), pyridine, tetra-chloroethane, and mixtures thereof. The choice of a suitable solvent or amixture of suitable solvents depends on the solubility of the sample ofthe UR in said solvents. If 75 mg of UR is soluble in 1 mL of deuteratedchloroform at 25° C., then deuterated chloroform is the solvent ofchoice for performing the ¹H-NMR spectroscopy for the UR. If a differentsolvent or mixture of solvents is used for performing the ¹H-NMR MethodWPU, then the chemical shifts of the protons of EX2 may shift from theones reported here for the selected solvents for the ¹H-NMR Method WPUsince the actual chemical shifts may depend on the solvent or mixture ofsolvents used to record the ¹H-NMR spectrum; in such case one shouldidentify and determine the chemical shifts of the corresponding protonsand apply EX2 for the determination of WPU.

The peak areas of the methine protons of pyrazine and methine protons (. . . —CH═ . . . ) of the vinyl groups ( . . . —CH═CH₂) in the VFUR orin the VU of EX2—as the case may be—were measured as follows: A sampleof 75 mg of VFUR or VU—as the case may be—was diluted at 40° C. in amixture of 0.200 ml methanol and 0.600 ml deuterated chloroformcontaining a known amount (mg) of pyrazine as internal standard forperforming ¹H-NMR spectroscopy. Subsequently, the ¹H-NMR spectrum of theVFUR or the VU sample—as the case may be—was recorded at 40° C. on a 400MHz BRUKER NMR-spectrometer. Afterwards, the chemical shifts (ppm) ofthe methine protons of pyrazine and the methine protons ( . . . —CH═ . .. ) of the vinyl groups ( . . . —CH═CH₂) in the VFUR or in the VU—as thecase may be—were identified; the chemical shifts (ppm) of the methineprotons of pyrazine and methine protons ( . . . —CH═ . . . ) of thevinyl groups ( . . . —CH═CH₂) in the VFUR or in the VU of EX2—as thecase may be—were measured on a 400 MHz BRUKER NMR-spectrometer inmethanol and deuterated chloroform were at about 8.6 and at about6.4-6.5 ppm, respectively. Subsequently, with the help of suitablecommercially available software for analyzing ¹H-NMR spectra such asACD/Spectrus Processor software provided by ACD/Labs, the peak areas ofthe methine protons of pyrazine and methine protons ( . . . —CH═ . . . )of the vinyl groups ( . . . —CH═CH₂) in the VFUR or in the VU of EX2—asthe case may be—were measured and from these values the WPU wasdetermined according to EX2.

If 75 mg of a VFUR or a VU—as the case may be—, are not soluble at 40°C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform,then any other suitable solvent or mixture of solvents known to theskilled person for performing the ¹H-NMR spectroscopy may be used; forexample DMSO (dimethyl sulfoxide), pyridine, tetra-chloro ethane, andmixtures thereof. The choice of a suitable solvent or a mixture ofsuitable solvents depends on the solubility of the sample of the VFUR ora VU—as the case may be—, in said solvents. If 75 mg of VFUR or VU—asthe case may be—, are soluble in a mixture of 0.200 ml methanol and0.600 ml deuterated chloroform at 40° C., then a mixture of methanol anddeuterated chloroform is the solvent of choice for performing the ¹H-NMRspectroscopy for the VFUR or the VU.

If a different solvent or mixture of solvents is used for performing the¹H-NMR Method WPU, then the chemical shifts of the protons of EX2 mayshift from the ones reported here for the selected solvents for the¹H-NMR Method WPU since the actual chemical shifts may depend on thesolvent or mixture of solvents used to record the ¹H-NMR spectrum; inaddition, one may perform the measurement at different temperature thanthe one disclosed herein, for example the measurement can be performedat higher temperature than the one disclosed herein in order tosolubilize the sample intended to be analyzed for measuring its WPUaccording to this method and/or may use a lower amount of sample e.g. 25mg, depending on the resolution of the NMR instrument; in such case oneshould identify and determine the chemical shifts of the correspondingprotons and apply EX2 for the determination of WPU.

The method—as described herein—for the measurement of the WPU of thesamples mentioned in the Examples, applies analogously for any UR andany VFUR, VU, taking of course into account common general knowledge inperforming and analyzing results of NMR spectroscopy, the particularchemical nature of the UR or the VFUR or the VU and the skills of oneskilled in the art of NMR spectroscopy; for example, the chemical shiftsmay be somewhat shifted from the ones disclosed herein, and/or thetemperatures used to perform the measurement different e.g. higher thanthe ones disclosed herein, or the amount of the sample used can be lowere.g. 25 mg, depending on the resolution of the NMR instrument; in suchcase one should identify and determine the chemical shifts of thecorresponding protons and apply EX2 for the determination of WPU.

1.2.6 DSC Method for the Measurement of T_(g), T_(m), T_(c), ΔH_(m),ΔH_(c), (Herein Abbreviated as ‘DSC Method’)

The glass transition temperature (T_(g) in ° C.), the crystallizationtemperature (T_(c) in ° C.), the crystallization enthalpy (ΔH_(c) inJ/g), the melting temperature (T_(m) in ° C.), the melting enthalpy(ΔH_(m) in J/g) were measured via Differential Scanning Calorimetry(DSC) on a TA instruments DSC Q2000 apparatus equipped with a coolingsystem TA instruments RCS90, in N₂ atmosphere calibrated with indium.The glass transition temperature, the crystallization temperature, thecrystallization enthalpy, the melting temperature, the melting enthalpy,of a chemical entity described in this application—to the extent thatthese parameters were applicable for said entity—were measured at anytime from 24 up to and including 72 hours from the time of thepreparation of said chemical entity. The processing of the signal (DSCthermogramme, Heat Flow vs. Temperature) was carried out using UniversalAnalysis 2000 software version 4.5a provided by TA instruments, asdescribed herein after:

A sample of 10±0.5 mg was weight and placed in the DSC cell. The samplewas cooled down to −20° C. and the temperature was kept at −20° C. for 1minute; upon 1 minute the sample was heated up to 200° C. at a heatingrate of 5° C./minute (thermograph A). Once the sample has reached 200°C., the temperature was maintained at 200° C. for 1 minute.Subsequently, the sample was cooled down to −90° C. at a cooling rate of5° C./minute (thermograph B); once the sample has reached −90° C., thetemperature was maintained at −90° C. for 1 minute. Subsequently, thesample was heated up to 150° C. at a heating rate of 5° C./minute(thermograph C) Thermographs A, B and C were processed as the Y axis ofthe thermographs representing the heat flow has exotherm up andendotherm down.

Thermograph A was used for measuring the glass transition temperature ofthe thermosetting powder coating composition (T_(g TPCC)).

Thermograph C was used for measuring the glass transition temperature ofthe UR (T_(g UR)).

Thermograph C was used for measuring the glass transition temperature ofthe VFUR (T_(g VFUR)).

Thermograph C was used for measuring the ΔH_(m), and T_(m).

Thermograph B was used to measure the ΔH_(c), T_(c).

The glass transition temperature was the midpoint temperature of thetemperature range over which the glass transition took place, saidmidpoint temperature was the point at which the curve was intersected bya line that was equidistant between the two extrapolated baselines, asdefined in § 3.2 and § 3.3 in ISO 11357-2 edition 1999-03-15 [formidpoint temperature see § 3.3.3 in ISO 11357-2; edition 1999-03-15].

The T_(m) was measured as the temperature recorded at the minimum heatflow of the endothermic signal attributed to the melting of the sample.

The ΔH_(m) was measured as the integrated heat flow over the temperaturerange of the metling.

The T_(c) was measured as the temperature recorded at the maximum heatflow of the exothermic signal attributed to the crystallization of thesample.

The ΔH_(c) was measured as the integrated heat flow over the temperaturerange of the crystallization.

1.2.7 Method to Determine Presence of Unreacted —N═C═O Groups (FreeIsocyanate Groups) (Herein Abbreviated as ‘Method NCO’)

An FT-IR spectrum was recorded on a Digilab Excalibur infraredspectrometer, using a Golden gate ATR accessory from Specac. FT-IRspectra were taken using a resolution of 4 cm⁻¹, over a range of 700cm⁻¹ to 4000 cm⁻¹ over 64 scans and processed with Varian Resolutionspro software version 5.1. A characteristic peak for unreacted —N═C═Ogroups can be found around 2250 cm⁻¹; the presence of this peak isindicative of unreacted —N═C═O groups (free isocyanate groups).

1.2.8 Measurement and Assessment of the Physical Storage Stability ofthe Thermosetting Powder Coating Compositions

The physical storage stability (PSS) of the thermosetting powder coatingcompositions of the invention was tested at 23° C. for 7 weeks (forresults see Table 3). Prior to assessing the PSS the thermosettingpowder coating composition was left to cool down to room temperature forabout 2-3 hours. The greater the extend of agglomeration or sinteringthe poorer the PSS, thus the lower its ranking according to thefollowing scale. The extent of agglomeration was visually assessed andranked according to the following rating on a 1-10 scale (1 representingthe worst PSS and 10 the best PSS):

10: No change.9: No agglomeration, very good fluidity.8: No agglomeration, good fluidity.7: Very low agglomeration; agglomeration can be dispersed by one lighttap into a fine powder.6: Very low agglomeration; agglomeration can be dispersed by severaltaps into a fine powder.5: Low agglomeration; agglomeration can be dispersed by hand pressureinto a fine powder.4: Low agglomeration; agglomeration cannot be dispersed by hand pressurein a fine powder.3: Severe agglomeration into several large lumps, material is pourable.2: Severe agglomeration into several large lumps, material is notpourable.1: product sintered to one lump, volume reduced.

1.2.9 Assessment of the Ability of a Thermosetting Powder CoatingComposition to Heat-Cure Fast at Low Temperature

The assessment of the ability of a thermosetting powder coatingcomposition to heat-cure fast at low temperature was performed preparinga powder coating of said thermosetting powder coating compositionaccording to § 4 in the Examples (‘Preparation of the powder coatings’)and then measuring the aceton double rubs that the thus prepared powdercoating withstood. If the powder coating was able to withstand 210 ADR,then the corresponding thermosetting powder coating composition was ableto heat-cure fast at low temperature (this is indicated as a ‘yes’ inthe corresponding examples). If the powder coating was not able towithstand 210 ADR, then the corresponding thermosetting powder coatingcomposition was not able to heat-cure fast at low temperature (this isindicated as a ‘no’ in the corresponding examples).

1.2.10 Methods for the Measurement of Properties of the Powder CoatingsObtained by Heat-Curing of the Thermosetting Powder Coating CompositionsPrepared Herein

The properties of the any and all of the powder coatings obtained byheat-curing of their corresponding thermosetting powder coatingcompositions were (and are to be) measured on the MDF substrates thatthey were applied on (see also ‘Preparation of the powder coatings’).Any and all properties of the powder coatings e.g. acetone double rubs(ADR), smoothness, coating (film) thickness, shown in the Examples, wereassessed upon heat-curing the corresponding thermosetting powder coatingcompositions (applied on MDF substrates) at low temperature, that isupon heat-curing at 95° C. for 3 minutes in a catalytic IR oven. Thetype of MDF substrates used was of Medite-MR type.

1.2.10.1 Smoothness

Smoothness (or also known in the art as flow) of powder coatingsobtained by heat cure of the corresponding thermosetting powder coatingcompositions, was determined by comparing the smoothness of the coatingwith PCI Powder Coating Smoothness panels (ACT Test Panels Inc.,APR22163 (A) Batch: 50708816) at a thickness of 100-120 μm. The ratingof smoothness is from 1 to 10, with 1 representing the roughest coatingand 10 representing the smoothest coating. By a rating of ‘<1’ is meantthat the smoothness of the powder coating was lower than the powdercoating smoothness panel with the lowest smoothness that of 1;effectively a powder coating with a smoothness <1 is a very rough powdercoating.

1.2.10.2 Coating (Film) Thickness

The coating (film) thickness of the powder coatings derived upon heatcuring of the corresponding thermosetting powder coating compositions,was measured with a Elcometer 195 Saberg Drill from Elcometer accordingto EN ISO 2808-5B:2007; the measurement was carried out on a coatedsurface of the coated MDF panel. The film thickness of any one of powdercoatings shown in the Examples and the Tables was in the range of from100 up to 120 μm; any and all properties measured herein concerningpowder coatings should be measured at this film thickness range.

1.2.10.3 Acetone Double Rubs (ADR)

With one aceton double rub (ADR) is meant one continuous back andforward movement, in a cycle time of about one second, over the surfaceof a powder coating having a thickness of 100-120 μm using a cottoncloth drenched in acetone, which cotton cloth covers a hammer headhaving a weight of about 980 grams and a contact surface area with thepowder coating of about 2 cm². Every 10 rubs the cloth was drenched inacetone. The measurement was carried out at room temperature, and it wasperformed on coatings that were left at room temperature for 24-48 hoursbefore been tested; the measurement was continued either until thecoating was removed and the number of ADR at which the coating wasremoved was reported, or until 500 ADR were reached. A result reportedas 500 ADR indicates that there was coating left after 500 ADR.

2. Synthesis of UR and Curing Agents 2.1 Synthesis of Unsaturated ResinsComprising Ethylenic Unsaturations (UR)

Table 1 presents the monomers used for the preparation of theunsaturated resins comprising ethylenic unsaturations said resins beingamorphous unsaturated polyester resin comprising 2-butenedioic acidethylenic unsaturations and the properties of said resins.

Amorphous (UR1-UR3) unsaturated polyesters comprising 2-butenedioic acidethylenic unsaturations were prepared.

All unsaturated polyester resins comprising 2-butenedioic acid ethylenicunsaturations (UR1-UR3) prepared herein were solid at room temperatureand at atmospheric pressure.

UR1

A reactor vessel fitted with a thermometer, a stirrer and a distillationdevice for the removal of water formed during the synthesis, was filledwith a tin catalyst (butyl stannoic acid, 1 g) and the monomers for thefirst step (isophthalic acid (320.1 g; 1.93 mol), neopentylglycol (314.5g; 3.02 mol) and hydrogenated bisphenol A (270.1 g; 1.12 mol) as listedin Table 1). Stirring was then applied and a light nitrogen flow waspassed over the reaction mixture while the temperature was raised to220° C.; the temperature was kept at 220° C. till no water was released.Subsequently, the reaction mixture was cooled down to 180° C.; once thetemperature reached 180° C. fumaric acid (231.6 g; 2.0 mol) togetherwith a small amount of t-butyl hydroquinone (0.2 g; 0.0012 mol) wasadded at a temperature of 180° C. followed by esterification at 205° C.(second step). When an acid value of less than 15 mg KOH/g resin wasreached and water stopped being released, the third step of thepolyester preparation was carried out under reduced pressure at 205° C.till an acid value of 6.5 mg KOH/g was reached. In order to lower theacid value of the resin below 5 mgKOH/g resin, 2,3-epoxy propylneodecanoate (7.7 g; 0.03 mol) was added to the resin in order to reactwith the acid groups of the resin; upon the addition of 2,3-epoxy propylneodecanoate the reaction continued for at least 30 minutes.Subsequently, the polyester resin was discharged onto an aluminum foilkept at room temperature. The polyester resin obtained had an acid valueof 4.7 mgKOH/g resin and a hydroxyl value of 35.7 mgKOH/g resin.

UR2

A reactor vessel fitted with a thermometer, a stirrer and a distillationdevice for the removal of water formed during the synthesis, was filledwith a tin catalyst (butyl stanoic acid, 1 g) and the monomers for thefirst step (terephthalic acid (553.7 g; 3.33 mol), trimethylol propane(44.1 g; 0.33 mol) and neopentyl glycol (443.4 g; 4.26 mol) as listed inTable 1). Stirring was then applied and a light nitrogen flow was passedover the reaction mixture while the temperature was raised to 220° C.;the temperature was kept at 220° C. till no water was released.Subsequently, the reaction mixture was cooled down to 180° C.; once thetemperature reached 180° C. fumaric acid (112.5 g; 0.92 mol) togetherwith a small amount t-butyl hydroquinone (0.1 g; 0.0006 mol) was addedat a temperature of 180° C. followed by esterification at 205° C.(second step). When an acid value of less than 15 mg KOH/g resin wasreached and water stopped being released, the third step of thepolyester preparation was carried out under reduced pressure at 205° C.till an acid value of 6.5 mg KOH/g was reached. In order to lower theacid value of the resin below 5 mgKOH/g resin, ethylene carbonate (5.6g; 0.06 mol) was added to the resin in order to react with the acidgroups of the resin; upon the addition of ethylene carbonate thereaction continued for at least 30 minutes. Subsequently, the polyesterresin was discharged onto an aluminum foil kept at room temperature. Thepolyester resin obtained had an acid value of 3.1 mgKOH/g resin and ahydroxyl value of 42.7 mgKOH/g resin.

UR3

A reactor vessel fitted with a thermometer, a stirrer and a distillationdevice for the removal of water formed during the synthesis, was filledwith a tin catalyst (butyl stannoic acid, 1 g) and the monomers for thefirst step (terephthalic acid (422 g; 2.54 mol), 1,2-propylene glycol(354.6 g; 4.66 mol), benzoic acid (92.8 g; 0.76 mol) and trimethylolpropane (18.8 g; 0.14 mol) as listed in Table 1). Stirring was thenapplied and a light nitrogen flow was passed over the reaction mixturewhile the temperature was raised to 220° C.; the temperature was kept at220° C. till no water was released. Subsequently, the reaction mixturewas cooled down to 180° C.; once the temperature reached 180° C. fumaricacid (220.5 g; 1.9 mol) together with a small amount of t-butylhydroquinone (0.1 g; 0.0006 mol) was added at a temperature of 180° C.followed by esterification at 205° C. (second step). When an acid valueof less than 15 mg KOH/g resin was reached and water stopped beingreleased, the third step of the polyester preparation was carried outunder reduced pressure at 205° C. till an acid value of 6.5 mg KOH/g wasreached. Subsequently, the polyester resin was discharged onto analuminum foil kept at room temperature. The polyester resin obtained hadan acid value of 1 mgKOH/g resin and a hydroxyl value of 52.6 mgKOH/gresin.

2.2 Synthesis of the Curing Agents

Vinyl functionalized urethane resins (VFUR) and vinyl urethanes (VU)were prepared and they were used as curing agents in the thermosettingpowder coating compositions prepared herein.

Table 2 presents the monomers used for the preparation of VFUR1, VFUR2,VU1, VU2 and VU3 and their properties.

Each of the VFUR1, VFUR2 was a crystalline vinyl ether functionalizedurethane resin (crystalline VEFUR).

VU1 was a crystalline vinyl ether urethane (crystalline VEU).

VU2 was a crystalline VEU-c; more particularly VU2 was diethylene glycoldivinyl ether urethane.

VU3 was a crystalline VEU-c; more particularly VU3 was triethyleneglycol divinyl ether urethane.

Each of VFUR1, VFUR2, VU1, VU2 and VU3 was crystalline, because each ofthem had a ΔH_(m)≥35 J/g.

The VFUR1 is not a curing agent A because it did not have any and all ofits melting temperatures within the T_(m) range of 30-80° C. The VFUR1had two melting temperatures, one at 98 and one at 107° C., thus both ofthem were outside the T_(m) range of 30-80° C.

The VFUR2 is not a curing agent A because it did not have any and all ofits melting temperatures within the T_(m) range of 30-80° C. The VFUR2had two melting temperatures, one at 74 and one at 84° C., thus one ofthem was outside the T_(m) range of 30-80° C.

The VU1 is not a curing agent A because it did not have any and all ofits melting temperatures within the T_(m) range of 30-80° C. The VU1 hada melting temperature at 100° C., which was outside the T_(m) range of30-80° C.

The VU2 is a curing agent A because it did have any and all of itsmelting temperatures within the T_(m) range of 30−80° C. The VU2 had twomelting temperatures, one at 69 and one at 76° C., thus any and all ofits T_(m) was within the T_(m) range of 30-80° C.

The VU3 is a curing agent A because it did have any and all of itsmelting temperatures within the T_(m) range of 30−80° C. The VU3 had onemelting temperature at 56° C., thus any and all of its T_(m) was withinthe T_(m) range of 30-80° C.

VFUR1

A reaction vessel fitted with a thermometer and a stirrer, was filledwith the monomers for the first step as listed in Table 2. Stirring wasthen applied and a light nitrogen flow was passed over the reactionmixture while the temperature was raised to approximately 60° C.Subsequently, for the second step an isocyanate as listed in Table 2 wasdosed such that the reaction mixture was kept below 120° C. duringaddition. After all isocyanate was dosed, the temperature was kept orset at 120° C. and maintained at this temperature for approximately halfan hour. The temperature was kept at 120° C. and vacuum was applied toremove all volatiles. After vacuum the content of the vessel wasdischarged.

VFUR2

A reaction vessel fitted with a thermometer, a stirrer and adistillation device for the removal of water formed during thesynthesis, was filled with a tin catalyst (butyl stannoic acid, 0.5 g)and the monomers for the first step (except 4-hydroxybutyl vinyl ether)as listed in Table 2. Stirring was then applied and a light nitrogenflow was passed over the reaction mixture while the temperature wasraised to 220 CC. The temperature was kept at 220° C. till an acid valueof approximately 10 mg KOH/g resin was reached and till no water wasbeing released. Subsequently, the temperature was lowered to 120° C. andas last monomer of the first step the 4-hydroxybutyl vinyl ether and atin catalyst (dibutyltin dilaurate, 0.5 g) were added at a temperatureof 120° C. Subsequently, for the second step the isocyanate as listed inTable 2 was dosed such that the reaction mixture was kept below 120° C.during addition. After all the isocyanate was dosed, the temperature waskept or set at 120° C. and maintained at this temperature forapproximately half an hour. The temperature was kept at 120° C. andvacuum was applied to remove all volatiles. After vacuum the content ofthe vessel was discharged.

VU1

A reaction vessel fitted with a thermometer and a stirrer, was filledwith the monomers for the first step as listed in Table 2. Stirring wasthen applied and a light nitrogen flow was passed over the reactionmixture while the temperature was raised to approximately 60° C.Subsequently, for the second step an isocyanate as listed in Table 2 wasdosed such that the reaction mixture was kept below 120° C. duringaddition. After all isocyanate was dosed, the temperature was kept orset at 120° C. and maintained at this temperature for approximately halfan hour. The temperature was kept at 120° C. and vacuum was applied forhalf an hour to remove all volatiles. Subsequently, n-butanol was addeduntil there were no unreactable isocyanate groups as evidenced by usingthe Method NCO, described herein. At 120° C. a vacuum was applied forhalf an hour to remove any residual n-butanol. After this period thecontent of the vessel was discharged.

VU2

A reaction vessel fitted with a thermometer and a stirrer, was filledwith the monomers for the first step as listed in Table 2. Stirring wasthen applied and a light nitrogen flow was passed over the reactionmixture while the temperature was raised to approximately 60° C.Subsequently, for the second step an isocyanate as listed in table 2 wasdosed such that the reaction mixture was kept below 100° C. duringaddition. After all isocyanate was dosed, the temperature was kept orset at 90° C. and maintained at this temperature for approximately halfan hour. The temperature was kept at 90° C. until there were nounreactable isocyanate groups as evidenced by using the Method NCO,described herein and then vacuum was applied for half an hour to removeall volatiles. After this period the content of the vessel wasdischarged.

VU3

A reaction vessel fitted with a thermometer and a stirrer, was filledwith the monomers for the first step as listed in Table 2. Stirring wasthen applied and a light nitrogen flow was passed over the reactionmixture while the temperature was raised to approximately 60° C.Subsequently, for the second step an isocyanate as listed in table 2 wasdosed such that the reaction mixture was kept below 100° C. duringaddition. After all isocyanate was dosed, the temperature was kept orset at 80° C. and maintained at this temperature for approximately halfan hour. The temperature was kept at 80° C. until there were nounreactable isocyanate groups as evidenced by using the Method NCO,described herein and then vacuum was applied for half an hour to removeall volatiles. After this period the content of the vessel wasdischarged.

3. Preparation of the Thermosetting Powder Coating Compositions

The preparation of the thermosetting powder coating compositions shownin the Examples and used for either the CompPCC or InvPCC was carriedout as follows: First the unsaturated resin comprising ethylenicunsaturation (UR) and the vinyl urethane or the vinyl functionalizedurethane resin—as the case may be—were mixed in a 90/10 ratio on weight(UR/VU or UR/VFUR as the case may be) in a blender; said mixture wassubsequently extruded in a PRISM TSE16 PC twin screw extruder at 120° C.with a screw speed of 200 rpm and a torque higher than 90%. The obtainedextrudate was allowed to cool to room temperature and broken into chips.Subsequently, the extrudate was placed in a blender, together with allother paint components, including any remaining VU or VFUR—as the casemay be—, making the formulations as listed in the corresponding Tables;subsequently, the mixture obtained was extruded in a PRISM TSE16 PC twinscrew extruder at 80° C. with a screw speed of 200 rpm and a torquehigher than 50%. The extrudate was allowed to cool at room temperatureand broken into chips. After approximately 12-16 hours these chips werethen ground in an ultra-centrifugal mill at 14000 rpm and sieved in aRetsch ZM100 sieve. The sieve fraction with particle size below 90 μmwas collected (by means of a Fritsch Analysette Spartan sievingapparatus equipped with a 90 micron sieve, sieving performed for 15minutes at 2.5 mm amplitude) and used for further processing.

Any one of the the thermosetting powder coating compositions describedin the Examples and shown in the relevant Tables, was white and had aparticle size lower than 90 microns.

Each of the thermosetting powder coating compositions according to theinvention shown in the Examples (InvPCC) had a glass transitiontemperature (T_(g)) of at least 25 and at most 70° C., wherein the T_(g)was measured via Differential Scanning Calorimetry (DSC) according to §1.2.6.

4. Preparation of the Powder Coatings

MDF substrates (type Medite-MR) were preheated at 60-70° C. using a gascatalytic IR oven from Vulcan. The thermosetting powder coatingcompositions CompPCC and InvPCC alike, prepared herein, wereelectrostatically sprayed (corona spray gun, 60 kV) onto the preheatedMDF substrates once the latter were brought out from the oven; thetemperature of MDF substrates during the electrostatic spraying was50-60° C. Subsequently, the coated MDF substrates were cured at 95° C.for 3 minutes in a catalytic IR oven (Vulcan) (without the applicationof radiation), affording white powder coatings.

TABLE 1 Composition and characterization of the unsaturated resinscomprising ethylenic unsaturations (UR) (each of the UR was anunsaturated polyester resin comprising 2-butenedioic acid ethylenicunsaturations). UR1 UR2 UR3 Monomers first step Isophthalic acid (mol)1.93 Terephthalic acid (mol) 3.33 2.54 Neopentylglycol (mol) 3.02 4.26Trimethylol propane (mol) 0.33 0.14 1,2-propylene glycol (mol) 4.66Benzoic acid 0.76 Hydrogenated bisphenol A (mol) 1.12 Monomers secondstep Fumaric acid (mol) 2 0.97 1.9 Total (mol) 8.07 8.89 10 Monomersfirst step Isophthalic acid (g) 320.1 Terephthalic acid (g) 553.7 631.6Neopentylglycol (g) 314.5 443.4 Trimethylol propane (g) 44.1 45.11,2-propylene glycol (g) 362.2 Hydrogenated bisphenol A (g) 270.1Monomers second step Fumaric acid (g) 231.6 112.5 114 Total weight (g)1136.3 1153.7 1152.9 Water formed during synthesis (g) 136.3 153.7 152.9Weight (g) of resin produced 1000 1000 1000 Properties &Characterisation amorphous amorphous amorphous WPU (g/mol) 536 1130 530M_(n) (Da) 3451 2798 3324 T_(g) (° C.) 53 47 43.2 Viscosity (Pa · s) @160° C. 41.1 21.2 4.0 AV (mg KOH/g UR) 4.7 3.1 6.5 OHV (mg KOH/g UR)35.7 42.7 12.8

TABLE 2 Composition and characterization of the vinyl functionalizedurethanes resins (VFUR) and vinyl urethanes (VU) used as curing agentsin the TPCC shown in the Examples. VFUR1 VFUR2 VU1 VU2 VU3 Monomersfirst step Hexane diol (mol) 0.32 Butane diol (mol) 0.05 4-Hydroxylbutylvinyl ether (mol) 4.53 2.83 4.8 diethylene glycol monovinylether 4.64triethylene glycol monovinylether 3.85 dodecane dioic acid 1.13ethyleneglycol 1.79 Monomers second step Hexamethylene diisocyanate 2.581.77 2.58 2.3 1.9 (mol) Total (mol) 7.43 7.52 7.43 6.94 5.76 Totalweight of reactants (g) 1000 1000 1000 1000 1000 Weight (g) of VFUR orVU 1000 1000 1000 1000 1000 produced crystaline crystaline crystalinecrystaline crystaline Properties & Characterisation VEFUR VEFUR VEUVEU-c VEU-c WPU (g/mol) 207 328 183 197 239 M_(n) (Da) 738 1053 656 685818 T_(g) (° C.) −59 — — — — T_(m) (° C.) (first melting 98 74 100 69 56temperature) T_(m) (° C.) (second melting 107 84 — 76 — temperature)ΔH_(m) (J/g) (associated to the 170 102 165 35 141 first meltingtemperature) ΔH_(m) (J/g) (associated to the 1.9 55 — 100 — secondmelting temperature) ΔH_(m) (J/g) (the sum of all 171.9 157 165 135 141ΔH_(m) associated to each of the melting temperatures) T_(c) (° C.) 8461 77 48 25 ΔH_(c) (J/g) 175 99 166 136 126 Viscosity (Pa · s) @ 160° C.<0.1 <0.1 <0.1 <0.1 <0.1 AV (mg KOH/g VU) 0 0 0 0 0 OHV (mg KOH/g VU) 00 0 0 0

TABLE 3 Composition and properties of comparative hermosetting powdercoating compositions and powder coatings thereof. CompPCC1 CompPCC2CompPCC3 CompPCC4 CompPCC5 CompPCC6 UR1 (g) 200 200 200 200 200 200VFUR1(g) 81.8 VU2 (g) 78.2 78.2 78.2 78.2 78.2 Perkadox ® PM-W75(g) 15.110.1 Laurox ® S (g) 16.6 Trigonox ® EHP (g) 14.5 9.6 Trigonox ® 23 (g)Trigonox ® 423 C70 (g) Perkadox ® 24 FL (g) 16.7 Trigonox ® C 50D PD (g)cobaltstearate (g) diphenyliodonium chloride (g) 2.7 2.7 2.7t-butylhydroquinone (g) 0.070 0.070 0.070 0.070 0.070 0.070 Kronos ®2310 (g) 84.5 83.5 83.5 83.5 83.5 83.5 Resiflow ® PV-5 (g) 4.2 4.2 4.24.2 4.2 4.2 K 1.06 1.06 1.06 1.06 1.06 1.06 Amount of component C(mmol/Kg A and B) 99.8 150.8 100.8 149.9 150.2 99.4 Amount of componentD (mmol/Kg A and B) 29.8 0.0 30.2 0.0 0.0 30.2 Amount of component E(mg/Kg A and B) 250 250 250 250 250 250 Properties of the thethermosetting powder coating compositions PSS 8 8 8 8 5 7 very good verygood very good very good good very good Able to heat-cure fast at lowtemperature no no no no no no Properties of the corresponding powdercoatings CompPC1 CompPC2 CompPC3 CompPC4 CompPC5 CompPC6 ChemicalResistance (ADR) (assessed upon 10 15 17 77 17 139 heat curing at 95°C./3 minutes) very poor very poor very poor very poor very poor poorSmoothness (PCI) (assessed upon heat curing <1 5 5 4 3 2 at 95^(θ)C/3minutes) poor sufficient sufficient sufficient sufficient sufficientComposition and properties of comparative hermosetting powder coatingcompositions and powder coatings thereof. CompPCC7 CompPCC8 CompPCC9CompPCC10 CompPCC11 UR1 (g) 200 200 200 200 200 VFUR1(g) VU2 (g) 78.278.2 78.2 78.2 78.2 Perkadox ® PM-W75(g) Laurox ® S (g) Trigonox ® EHP(g) Trigonox ® 23 (g) 10.2 6.8 Trigonox ® 423 C70 (g) 11.9 17.9Perkadox ® 24 FL (g) Trigonox ® C 50D PD (g) 16.2 cobaltstearate (g)0.87 diphenyliodonium chloride (g) 2.7 2.7 t-butylhydroquinone (g) 0.0700.070 0.070 0.070 0.070 Kronos ® 2310 (g) 83.5 83.5 83.5 83.5 83.5Resiflow ® PV-5 (g) 4.2 4.2 4.2 4.2 4.2 K 1.06 1.06 1.06 1.06 1.06Amount of component C (mmol/Kg A and B) 150.3 100.2 98.0 99.6 149.8Amount of component D (mmol/Kg A and B) 0.0 30.2 0.0 30.2 0.0 Amount ofcomponent E (mg/Kg A and B) 250 250 250 250 250 Properties of the thethermosetting powder coating compositions PSS 6 8 8 1 1 good very goodvery good very poor very poor Able to heat-cure fast at low temperatureno no no no no Properties of the corresponding powder coatings CompPC7CompPC8 CompPC9 CompPC10 CompPC11 Chemical Resistance (ADR) (assessedupon 12 35 42 8 63 heat curing at 95° C./3 minutes) very poor very poorvery poor very poor very poor Smoothness (PCI) (assessed upon heatcuring 4 4 4 <1 1 at 95^(θ)C/3 minutes) sufficient sufficient sufficientpoor poor

TABLE 4 Composition and properties of inventive thermosetting powdercoating compositions and powder coatings thereof. InvPCC1 InvPCC2InvPCC3 InvPCC4 InvPCC5 InvPCC6 UR1 (g) 200 200 200 200 200 200 VFUR1(g)VU2 (g) 78.2 78.2 78.2 78.2 78.2 78.2 Perkadox ® PM-W75(g) Perkadox ® 26(g) 22.4 15 Perkadox ® 16 (g) 14.2 9.4 Perkadox ® 24 FL (g) 24.8 16.6diphenyliodoniunn chloride (g) 2.7 2.7 2.7 t-butylhydroquinone (g) 0.0700.070 0.070 0.070 0.070 0.070 Kronos ® 2310 (g) 83.5 83.5 83.5 83.5 83.583.5 Resiflow ® PV-5 (g) 4.2 4.2 4.2 4.2 4.2 4.2 K 1.06 1.06 1.06 1.061.06 1.06 Amount of component C (mmol/Kg A and B) 150.2 150.6 150.1100.6 99.7 100.5 Amount of component D (mmol/Kg A and B) 0.0 0.0 0.030.2 30.2 30.2 Amount of component E (mg/Kg A and B) 250 250 250 250 250250 Properties of the the thermosetting powder coating compositions PSS8 7 8 8 8 8 very good very good very good very good very good very goodAble to heat-cure fast at low temperature yes yes yes yes yes yesProperties of the corresponding powder coatings InvPC1 InvPC2 InvPC3InvPC4 InvPC5 InvPC6 Chemical Resistance (ADR) (assessed upon heat 500500 500 500 500 500 curing at 95° C./3 minutes) excellent excellentexcellent excellent excellent excellent Smoothness (PCI) (assessed uponheat curing 4 4 5 3 3 3 at 95^(θ)C/3 minutes) sufficient sufficientsufficient sufficient sufficient sufficient

TABLE 5 Composition and properties of comparative thermosetting powdercoating compositions and powder coatings thereof. CompPCC12 CompPCC13CompPCC14 CompPCC15 CompPCC16 UR1 (g) 200 200 200 UR2 (g) 200 UR3 (g)200 VFUR1 (g) 81.8 81.8 VU1 (g) 41.4 82.8 VFUR2 (g) 133.1 Perkadox ®PM-W75 10.1 (g) Perkadox ® 26 (g) 12.4 Perkadox ® 16 (g) 6.7 Perkadox ®24 FL (g) 16.7 19.8 diphenyliodonium 2.7 2.7 3.2 chloride (g)t-butylhydroquinone (g) 0.070 0.070 0.083 0.060 0.071 Kronos ® 2310 (g)84.5 84.5 99.9 72.4 84.8 Resiflow ® PV-5 (g) 4.2 4.2 5.0 3.6 4.2 K 1.201.20 1.09 1.13 1.06 Amount of component C 100 100 100 82 82 (mmol/Kg Aand B) Amount of component D 29.8 29.8 29.9 0.0 0.0 (mmol/Kg A and B)Amount of component E 250 250 250 250 250 (mg/Kg A and B) Properties ofthe the thermosetting powder coating compositions PSS 8 8 8 2 3 verygood very good very good poor mediocre Able to heat-cure fast no no nono no at low temperature Properties of the corresponding powder coatingsCompPC12 CompPC13 CompPC14 CompPC15 CompPC16 Chemical Resistance 10 17 813 24 (ADR) (assessed upon very poor very poor very poor very poor verypoor heat curing at 95° C./ 3 minutes) Smoothness (PCI) 1 0 0 0 1(assessed upon heat poor poor poor poor poor curing at 95^(⊖) C./ 3minutes)

TABLE 6 Composition and properties of inventive thermosetting powdercoating compositions and powder coatings thereof. InvPCC7 InvPCC8InvPCC9 InvPCC10 UR1 (g) 200 200 UR2 (g) 200 UR3 (g) 200 VU2 (g) 41.478.2 78.2 VU3 (g) 96.5 Perkadox ® 26 (g) 12.4 Perkadox ® 16 (g) 6.7Perkadox ® 24 FL (g) 16.7 17 diphenyliodonium 2.7 2.7 chloride (g)t-butylhydroquinone (g) 0.060 0.070 0.070 0.074 Kronos ® 2310 (g) 72.484.8 83.5 89.0 Resiflow ® PV-5 (g) 3.6 4.2 4.2 4.4 K 1.19 1.05 1.06 1.31Amount of component C 82 82 101 97 (mmol/Kg A and B) Amount of componentD 0.0 0.0 30.2 28.4 (mmol/Kg A and B) Amount of component E 250 250 250250 (mg/Kg A and B) Properties of the the thermosetting powder coatingcompositions PSS 7 7 8 7 very very very very good good good good Able toheat-cure fast at yes yes yes yes low temperature Properties of thecorresponding powder coatings InvPC7 InvPC8 InvPC9 InvPCIO ChemicalResistance 500 500 500 500 (ADR) (assessed upon heat excellent excellentexcellent excellent curing at 95° C./3 minutes) Smoothness (PCI) 3 5 4 4(assessed upon heat curing sufficient sufficient sufficient sufficientat 95^(⊖) C./3 minutes)

TABLE 7 Composition and properties of comparative thermosetting powdercoating compositions and powder coatings thereof. CompPCC17 CompPCC18CompPCC19 UR1 (g) 200 200 200 VU2 (g) 78.2 78.2 78.2 Perkadox ® 24 FL(g) 4.2 4.2 diphenyliodonium 8.9 4.2 chloride (g) t-butylhydroquinone(g) 0.070 0.070 0.070 Kronos ® 2310 (g) 83.5 83.5 83.5 Resiflow ® PV-5(g) 4.2 4.2 4.2 K 1.07 1.07 1.07 Amount of component C 0 25 25 (mmol/KgA and B) Amount of component D 100 0 47 (mmol/Kg A and B) Amount ofcomponent E 250 250 250 (mg/Kg A and B) Properties of the thethermosetting powder coating compositions PSS 8 9 8 very good very goodvery good Able to heat-cure fast at no no no low temperature Propertiesof the corresponding powder coatings CompPC17 CompPC18 CompPC19 ChemicalResistance 23 12 27 (ADR) (assessed upon very poor very poor very poorheat curing at 95° C./3 minutes) Smoothness (PCI) 7 5 3 (assessed uponheat curing sufficient sufficient sufficient at 95^(⊖) C./3 minutes)

TABLE 8 Composition and properties of inventive thermosetting powdercoating compositions and powder coatings thereof. InvPCC11 InvPCC12InvPCC13 InvPCC14 InvPCC15 InvPCC16 InvPCC17 InvPCC18 UR1 (g) 200 200200 200 200 200 200 200 VU2 (g) 78.2 78.2 78.2 78.2 78.2 78.2 78.2 78.2Perkadox ® 24 FL (g) 8.4 8.4 16.5 16.5 16.5 16.5 24.9 33diphenyliodonium chloride (g) 4.2 4.2 1.3 2.7 4.2 t-butylhydroquinone(g) 0.070 0.014 0.070 0.070 0.070 0.070 0.070 0.070 Kronos ® 2310 (g)83.5 83.5 83.5 83.5 83.5 83.5 83.5 83.5 Resitlow ® PV-5 (g) 4.2 4.2 4.24.2 4.2 4.2 4.2 4.2 K 1.07 1.07 1.07 1.07 1.07 1.07 1.07 1.07 Amount ofcomponent C (mmol/Kg A and B) 51 51 100 100 100 100 151 200 Amount ofcomponent D (mmol/Kg A and B) 47 47 0 15 30 47 0 0 Amount of component E(mg/Kg A and B) 250 50 250 250 250 250 250 250 Properties of the thethermosetting powder coating compositions PSS 8 8 8 8 8 8 8 8 very goodvery good very good very good very good very good very good very goodAble to heat-cure fast at low temperature yes yes yes yes yes yes yesyes Properties of the corresponding powder coatings InvPC11 InvPC12InvPC13 InvPC14 InvPC15 InvPC16 InvPC17 InvPC18 Chemical Resistance(ADR) (assessed upon heat 500 500 500 500 500 500 500 500 curing at 95°C./3 minutes) excellent excellent excellent excellent excellentexcellent excellent excellent Smoothness (PCI) (assessed upon heatcuring at 3 2 4 4 4 3 4 2 95^(θ)C/3 minutes) sufficient sufficientsufficient sufficient sufficient sufficient sufficient sufficient

TABLE 9 Composition and properties of inventive thermosetting powdercoating compositions and powder coatings thereof. InvPCC19 InvPCC20InvPCC21 InvPCC22 UR1 (g) 200 200 200 200 VU3 (g) 94.5 130 165 200Perkadox ® 24 FL (g) 17.5 19.6 21.6 23.7 diphenyliodonium 4.7 5.4 5.86.3 chloride (g) t-butylhydroquinone (g) 0.074 0.083 0.091 0.100Kronos ® 2310 (g) 88.4 99.0 109.5 120.0 Resiflow ® PV-5 (g) 4.4 5.0 5.56.0 K 1.06 1.46 1.85 2.24 Amount of component C 100 100 100 100 (mmol/KgA and B) Amount of component D 50 51 50 49 (mmol/Kg A and B) Amount ofcomponent E 250 250 250 250 (mg/Kg A and B) Properties of the thethermosetting powder coating compositions PSS 8 8 7 7 very good verygood very good very good Able to heat-cure fast at yes yes yes yes lowtemperature Properties of the corresponding powder coatings InvPC19InvPC20 InvPC21 InvPC22 Chemical Resistance 500 500 500 500 (ADR)(assessed upon excellent excellent excellent excellent heat curing at95° C./3 minutes) Smoothness (PCI) 3 4 7 9 (assessed upon heatsufficient sufficient sufficient sufficient curing at 95^(⊖) C./3minutes)

TABLE 10 Composition and properties of inventive and comparativethermosetting powder coating compositions and powder coatings thereof.CompPCC20 InvPCC23 InvPCC24 InvPCC25 InvPCC26 InvPCC27 CompPCC21 UR1 (g)200 200 200 200 200 200 200 VU3 (g) 94.6 94.6 94.6 94.6 94.6 94.6 94.6Perkadox ® 24 FL (g) 4.2 8 8.7 17.5 34.9 52.3 96 t-butylhydroquinone (g)0.074 0.074 0.074 0.074 0.074 0.074 0.074 Kronos ® 2310 (g) 88.4 88.488.4 88.4 88.4 88.4 88.4 Resiflow ® PV-5 (g) 4.4 4.4 4.4 4.4 4.4 4.4 4.4K 0.98 0.98 0.98 0.98 0.98 0.98 0.98 Amount of component C (mmol/Kg Aand B) 24 46 50 100 199 299 549 Amount of component D (mmol/Kg A and B)0 0 0 0 0 0 0 Amount of component E (mg/Kg A and B) 250 250 250 250 250250 250 Properties of the the thermosetting powder coating compositionsPSS 8 8 8 8 8 8 6 very good very good very good very good very good verygood good Able to heat-cure fast at low temperature no yes yes yes yesyes no Properties of the corresponding powder coatings CompPC20 InvPC23InvPC24 InvPC25 InvPC26 InvPC27 CompPC21 Chemical Resistance (ADR)(assessed 5 500 500 500 500 500 132 upon heat curing at 95° C./3minutes) very poor excellent excellent excellent excellent excellentpoor Smoothness (PCI) (assessed upon heat curing at 6 5 5 5 4 2 <195^(θ)C/3 minutes) sufficient sufficient sufficient sufficientsufficient sufficient poor

TABLE 11 Composition and properties of inventive thermosetting powdercoating compositions and powder coatings thereof. InvPCC28 InvPCC29InvPCC30 InvPCC31 UR1 (g) 200 200 200 200 VFUR2 (g) 10 4 VU3 (g) 82 9068 94.6 Perkadox ® 24 FL 34.5 35.3 31.7 34.9 (g) t-butylhydroquinone0.073 0.074 0.067 0.221 (g) Kronos ® 2310 (g) 87.6 88.2 80.4 88.4Resiflow ® PV-5 (g) 4.4 4.4 4.0 4.4 K 0.98 0.98 0.70 0.98 Amount of 199202 199 199 component C (mmol/Kg A and B) Amount of 0 0 0 0 component D(mmol/Kg A and B) Amount of 250 250 250 750 component E (mg/Kg A and B)Properties of the the thermosetting powder coating compositions PSS 8 88 8 very good very good very good very good Able to heat-cure fast yesyes yes yes at low temperature Properties of the corresponding powdercoatings InvPC28 InvPC29 InvPC30 InvPC31 Chemical Resistance 500 500 500500 (ADR) (assessed ecellent excellent excellent excellent upon heatcuring at 95° C./3 minutes) Smoothness (PCI) 3 4 2 5 (assessed upon heatsuffient sufficient sufficient sufficient curing at 95^(⊖) C./3 minutes)

Only the Inventive Examples (thermosetting powder coating compositionsaccording to the invention of claim 1; also referred as inventive TPCC)had in combination all features of claim 1. It was surprisingly foundthat only the inventive TPCC were able to provide for a uniquecombination of much desired properties. More specifically, only theinventive TPCC were heat curable and were able to heat-cure fast at lowtemperature and said heat curable thermosetting powder coatingcompositions upon heat-curing at low temperature were able to producepowder coatings having at least good, preferably very good, morepreferably excellent chemical resistance. Actually, all the inventiveTPCC were heat curable and were able to heat-cure fast at lowtemperature and said heat curable thermosetting powder coatingcompositions upon heat-curing at low temperature were able to producepowder coatings having excellent chemical resistance. Thus, only theinventive TPCC met the primary object of the invention.

In addition, only the inventive TPCC were heat curable and were able toheat-cure fast at low temperature, had very good physical storagestability and said heat curable thermosetting powder coatingcompositions upon heat-curing at low temperature were able to producepowder coatings having at least good, preferably very good, morepreferably excellent chemical resistance. Furthermore, only theinventive TPCC were heat curable and were able to heat-cure fast at lowtemperature, had very good physical storage stability, and said heatcurable thermosetting powder coating compositions upon heat-curing atlow temperature were able to produce powder coatings having: i)excellent chemical resistance, and ii) at least sufficient smoothness.

None of the Comparative Examples had in combination all features ofclaim 1. Any and all Comparative Examples failed even to meet theprimary object of the invention, let alone the additional surprisingarray of very desirable as explained and shown in this application.

The invention of claim 1 constitutes a noticeable progress over theprior art and it contributes a great deal to the advancement andprogress of the technology of thermosetting powder coatings. The reasonbeing the invention of claim 1 makes feasible the achievement of heatcurable thermosetting powder coating compositions that were able toheat-cure fast at low temperature and said heat curable thermosettingpowder coating compositions upon heat-curing at low temperature wereable to produce powder coatings having at least good, preferably verygood, more preferably excellent chemical resistance. Actually, all theinventive TPCC were heat curable and were able to heat-cure fast at lowtemperature and said heat curable thermosetting powder coatingcompositions upon heat-curing at low temperature were able to producepowder coatings having excellent chemical resistance. In addition theinventive thermosetting powder coating compositions were able at thesame time to achieve a further fantastic and unique array of verydesirable properties as explained and shown in this application.

1. A thermosetting powder coating composition comprising the followingcomponents A to C: A: one or more unsaturated resins comprisingethylenic unsaturations (UR) selected from the group consisting ofpolyester resins, acrylic resins, polyurethanes, epoxy resins,polyamides, polyesteramides, polycarbonates, polyureas and mixturesthereof, and B: one or more curing agents selected from the groupconsisting of vinyl urethanes, vinyl functionalized urethane resins andmixtures thereof, wherein at least one curing agent is curing agent Awhich is selected from the group consisting of i), ii) and iii): i) oneor more crystalline VU-c each of which is a crystalline vinyl urethanehaving a melting enthalpy ΔH_(m)≥35 J/g, and one or more meltingtemperatures (T_(m)) wherein any and all of the T_(m) of the one or morecrystalline VU-c are in the region of from and including 30 up to andincluding 80° C., and ii) one or more crystalline VFUR-c each of whichis a crystalline vinyl functionalized urethane resin having a meltingenthalpy ΔH_(m)≥35 J/g, and one or more melting temperatures (T_(m))wherein any and all of the T_(m) of the one or more crystalline VFUR-care in the region of from and including 30 up to and including 80° C.,and iii) mixtures of crystalline VU-c and crystalline VFUR-c, whereinthe ΔH_(m) and T_(m) is each measured via Differential ScanningCalorimetry (DSC) according to the description, and C: one or morethermal radical initiators, wherein at least one thermal radicalinitiator is peroxydicarbonate-X which is present in an amount of atleast 26 and at most 500 mmol/Kg A and B, and wherein theperoxydicarbonate-X is selected from the group consisting ofperoxydicarbonates represented by the following formula X, and mixturesthereof,

wherein R₁ is C₉-C₂₂ saturated hydrocarbyl, and R₂ is C₉-C₂₂ saturatedhydrocarbyl.
 2. The thermosetting powder coating composition accordingto claim 1, wherein the peroxydicarbonate-X is present in an amount ofat most 400 mmol/Kg A and B.
 3. The thermosetting powder coatingcomposition according to claim 1, wherein the peroxydicarbonate-X ispresent in an amount of at most 350 mmol/Kg A and B.
 4. Thethermosetting powder coating composition according to claim 1, whereinthe peroxydicarbonate-X is present in an amount of at most 300 mmol/Kg Aand B.
 5. The thermosetting powder coating composition according toclaim 1, wherein the peroxydicarbonate-X is present in an amount of atleast 30 mmol/Kg A and B.
 6. The thermosetting powder coatingcomposition according to claim 1, wherein the peroxydicarbonate-X ispresent in an amount of at least 40 mmol/Kg A and B.
 7. Thethermosetting powder coating composition according to claim 1, whereinthe peroxydicarbonate-X is present in an amount of at least 45 mmol/Kg Aand B.
 8. The thermosetting powder coating composition according toclaim 1, wherein the total amount of the component C is at most 500mmol/Kg A and B.
 9. The thermosetting powder coating compositionaccording to claim 2, wherein the total amount of the component C is atmost 400 mmol/Kg A and B.
 10. The thermosetting powder coatingcomposition according to claim 3, wherein the total amount of thecomponent C is at most 350 mmol/Kg A and B.
 11. The thermosetting powdercoating composition according to claim 4, wherein the total amount ofthe component C is at most 300 mmol/Kg A and B.
 12. The thermosettingpowder coating composition according to claim 1, wherein theperoxydicarbonate-X is selected from the group consisting of dimyristylperoxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetylperoxydicarbonate, and mixtures thereof.
 13. The thermosetting powdercoating composition according to claim 1, wherein B is present in anamount of at least 15 and at most 55 pph of A and B.
 14. Thethermosetting powder coating composition according to claim 1, whereinthe curing agent A is present in an amount of at least 70 pph of B. 15.The thermosetting powder coating composition according to claim 1,wherein the curing agent A is present in an amount of at least 80 pph ofB.
 16. The thermosetting powder coating composition according to claim1, wherein K being the ratio of the total mol of the ethylenicunsaturations in B divided to the total mol of the ethylenicunsaturations in A, is at least 0.6 and at most
 3. 17. The thermosettingpowder coating composition according to claim 1, wherein K being theratio of the total mol of the ethylenic unsaturations in B divided tothe total mol of the ethylenic unsaturations in A, is at least 0.95 andat most 2.5.
 18. The thermosetting powder coating composition accordingto claim 1, wherein the curing agent A has a crystallization temperature(T_(c)) of at least 10 and at most 70° C., wherein the T_(c) is measuredvia Differential Scanning Calorimetry (DSC) according to thedescription.
 19. The thermosetting powder coating composition accordingto claim 1, wherein the thermosetting powder coating composition furthercomprises component D, wherein D: one or more co-initiators selectedfrom the group consisting of onium compounds, sulpho compounds, andmixtures thereof, and wherein the component D is present in an amount ofat most 95 mmol/Kg A and B.
 20. The thermosetting powder coatingcomposition according to claim 1, wherein the thermosetting powdercoating composition further comprises component D, wherein D: one ormore co-initiators selected from the group consisting of oniumcompounds, sulpho-compounds, and mixtures thereof, and wherein the oniumcompounds are selected from the group consisting of compoundsrepresented by the following formula I-X and compounds represented bythe following formula II-X

wherein A⁻ is selected from the group consisting of halide anions; andR₁′″ is a C₁-C₁₂ saturated hydrocarbyl, and R₂′″ is a C₁-C₁₂ saturatedhydrocarbyl; and wherein the component D is present in an amount of atmost 95 mmol/Kg A and B.
 21. The thermosetting powder coatingcomposition according to claim 1, wherein the thermosetting powdercoating composition further comprises component E, wherein E: one ormore inhibitors selected from the group consisting of phenoliccompounds, stable radicals, catechols, phenothiazines, hydroquinones,benzoquinones and mixtures thereof, and wherein the total amount ofcomponent E is at least 20 and at most 1500 mg/Kg A and B.
 22. Thethermosetting powder coating composition according to claim 1, whereinthe UR is an unsaturated polyster resin comprising 2-butenedioic acidethylenic unsaturations.
 23. The thermosetting powder coatingcomposition according to claim 1, wherein the UR has: a) a numberaverage molecular weight (M_(n)) of at least 1000 and at most 10000 Da,and b) a glass transition temperature (T_(g)) of at least 40 and at most75° C., and c) a weight per unsaturation (WPU) of at least 250 and atmost 2200 g/mol, and wherein the M_(n) is measured via Gel PermeationChromatography (GPC) according to the description, the T_(g) is measuredvia Differential Scanning Calorimetry (DSC) according to the descriptionand the WPU is measured via ¹H-NMR spectroscopy according to thedescription.
 24. The thermosetting powder coating composition accordingto claim 1, wherein the curing agent A which is selected from the groupconsisting of i), ii) and iii): i) one or more crystalline VU-c each ofwhich is a crystalline vinyl urethane having a melting enthalpyΔH_(m)≥35 J/g, and one or more melting temperatures (T_(m)) wherein anyand all of the T_(m) of the one or more crystalline VU-c are in theregion of from and including 45 up to and including 78° C., and a numberaverage molecular weight (M_(n)) of at least 660 and at most 1200 Da,and ii) one or more crystalline VFUR-c each of which is a crystallinevinyl functionalized urethane resin having a melting enthalpy ΔH_(m)≥35J/g, and one or more melting temperatures (T_(m)) wherein any and all ofthe T_(m) of the one or more crystalline VFUR-c are in the region offrom and including 45 up to and including 78° C., and a number averagemolecular weight (M_(n)) of at least 660 and at most 1200 Da, and iii)mixtures of crystalline VU-c and crystalline VFUR-c, wherein the M_(n)is measured via Gel Permeation Chromatography (GPC) according to thedescription.
 25. The thermosetting powder coating composition accordingto claim 1, wherein the curing agent A is selected from the groupconsisting of crystalline VEU-c.
 26. The thermosetting powder coatingcomposition according to claim 1, wherein the curing agent A is selectedfrom the group consisting of diethylene glycol divinyl ether urethane,triethylene glycol divinyl ether urethane, and mixtures thereof.
 27. Thethermosetting powder coating composition according to claim 1, whereinthe thermosetting powder coating composition has a glass transitiontemperature (T_(g)) of at least 25 and at most 70° C., wherein the T_(g)is measured via Differential Scanning Calorimetry (DSC) according to thedescription.
 28. The thermosetting powder coating composition accordingto claim 1, wherein the curing agent A has a T_(c) which is lower thanits T_(m) and preferably the T_(c) of the curing agent is at most 55° C.lower than its T_(m), or lower than its highest T_(m) if the curingagent A has more than one T_(m).
 29. A process for making athermosetting powder coating composition as defined in claim 1, saidprocess comprising the steps of: a. mixing the components of thethermosetting powder coating composition to obtain a premix; b. heatingthe premix in an extruder up to and including the decompositiontemperature of the component C, to obtain an extrudate; c. cooling downthe extrudate to obtain a solidified extrudate; and d. grinding thesolidified extrudate into smaller particles to obtain the thermosettingpowder coating composition.
 30. A cured thermosetting powder coatingcomposition obtained by curing a thermosetting powder coatingcomposition as defined in claim
 1. 31. An article having coated thereona thermosetting powder coating composition as defined in claim
 1. 32. Anarticle having coated and cured thereon a thermosetting powder coatingcomposition as defined in claim
 1. 33. A process for making a coatedarticle, said process comprising the steps of: applying a thermosettingpowder coating composition as defined in claim 1 to an article, andheating and/or radiating the thermosetting powder coating compositionfor enough time and at a suitable temperature to cure the thermosettingpowder coating composition, to obtain the coated article.
 34. Use of: athermosetting powder coating composition as defined in claim 1; or acured thermosetting powder coating composition; or an article, in powdercoatings, powder coatings for heat-sensitive articles, powder coatingsfor non-heat-sensitive articles, 3D-printing, automotive applications,marine applications, aerospace applications, medical applications,defense applications, sports/recreational applications, architecturalapplications, bottling applications, household applications, machineryapplications, can applications, coil applications, energy applications,textile applications and electrical applications.